CN1778871A - High-dispersion iron catalyst by direct coal hydrogenation liquefaction - Google Patents
High-dispersion iron catalyst by direct coal hydrogenation liquefaction Download PDFInfo
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- CN1778871A CN1778871A CN 200410091152 CN200410091152A CN1778871A CN 1778871 A CN1778871 A CN 1778871A CN 200410091152 CN200410091152 CN 200410091152 CN 200410091152 A CN200410091152 A CN 200410091152A CN 1778871 A CN1778871 A CN 1778871A
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Abstract
A hydrogenation liquefied high-dispersion iron catalyst from coal consists of active component gamma-FeOOH with Fe content 1~15wt%(dry base), carrier coal 50~90wt%(dry base) and impurity water residue. The gamma-FeOOH is distributed in liquefied coal with strip shape, grain size range 60~200nm and width 20~100nm. It is cheap, high efficient and easy storage, has small size, high catalyst activity and various resources.
Description
Technical field
A kind of high-dispersion iron catalyst that is used for the coal Direct Hydrogenation liquefaction belongs to the coal chemistry manufacture field, specifically, is a kind of high-dispersion iron catalyst product that is used for the coal Direct Hydrogenation liquefaction.
Background technology
Coal resources in China is abundant relatively, and the petroleum resources relative shortage.Domestic petroleum consumption increases fast, and the petroleum resources of China can not satisfy the needs of growing oil consumption.Since China in 1993 became clean oil importers, the petroleum import amount of China increased year by year, and China in 2003 comprises that the petroleum import amount of crude oil and processed oil is above 100,000,000 tons.China's development direct coal liquefaction technology realizes that the DCL/Direct coal liquefaction industrialization is to solve one of approach of China's oil shortage.
DCL/Direct coal liquefaction be coal under the effect of certain temperature and pressure condition and catalyzer, change the process of liquid fuel and other chemical into through hydrogenation, be a kind of of the clean process and utilization technology of coal.DCL/Direct coal liquefaction is once industrialized technology, development through a nearly century, direct coal liquefaction technology has significant progress again, its reaction conditions of the direct coal liquefaction technology of Kai Fa a new generation relaxes more the most in the last thirty years, liquid product yield is higher, has reached industrialized once more condition under the feasible prerequisite of Technological Economy substantially.In order to realize the industrialization under the direct coal liquefaction technology economically feasible prerequisite, a kind of efficient and cheap catalyzer of development and utilization is very important.
The DCL/Direct coal liquefaction catalyzer can be divided three classes, and the first kind is a noble metal catalyst, as cobalt, molybdenum, nickel catalyzator; Second class is a metal halide catalyst, as ZnCl
2And SnCl
2Deng; The 3rd class is iron system abandoning a property catalyzer, as ferruginous natural mineral, industrial residue and synthetic iron containing compounds etc.Studies show that noble metal catalyst is active high, is widely used in oil hydrofining field.But this class catalyzer costs an arm and a leg, and needs repeated regeneration to use, and coal liquefaction system is difficult to realize the recovery and the regeneration of catalyzer, so this class catalyzer is difficult to be applied to coal hydrogenation liquefaction.Belong to halide catalyst for belonging to the strong acid type catalyzer, scission reaction is had stronger katalysis, but gelatin liquefaction equipment is had stronger corrosive nature, in fact this class catalyzer also is difficult to the industrialization use.Fe-series catalyst once uses and need not reclaim because wide material sources are cheap, discharges with coal liquefaction residue, and environment is not constituted extra influence, and other two kinds of catalyzer have high cost performance relatively, thereby receive great concern.It also is the direction of Catalysts for Direct Coal Liquefaction and development.
Commonly used in the Fe-series catalyst have natural iron-bearing mineral matter such as pyrite (pyrite), limonite (limonite) and industrial residue such as a red mud (aluminium making residue) etc., this class Fe-series catalyst is owing to be difficult to disperse, its granularity is many at micron order, so catalytic effect has limitation, addition is also more than 3%.Reducing size of catalyst is one of active important means that improves Fe-series catalyst, and the conventional catalyst size that obtains with the method for mechanical mill need consume many energy, and the granularity of catalyzer also can only be about 1 micron.The various countries scientist has also attempted the Fe-series catalyst that many other methods obtain the high dispersive ultra-fine grain, but because preparation cost is higher, is difficult to large-scale industrial production.
Summary of the invention
The objective of the invention is for DCL/Direct coal liquefaction provides a kind of effective catalyst, this catalyzer is that a kind of fine particle, γ-FeOOH are main, high dispersing abandoning property of the iron-based coal hydrogenation liquefaction catalyzer on the liquefaction coal surface.
Abandoning property of coal Direct Hydrogenation liquefaction high dispersive iron-based catalyzer of the present invention is to be made of active ingredient γ-FeOOH, carrier coal and moisture impurity three parts.Active ingredient is γ-FeOOH, and wherein Fe content is the 1～15wt% (butt) of catalyzer, and relatively Shi Yi Fe content is the 1～8wt% (butt) of catalyzer; Carrier is a liquefaction coal itself, and the content of carrier coal is the 50～90wt% (butt) of catalyzer, and relatively Shi Yi carrier coal content is the 60～80wt% (butt) of catalyzer, and all the other components are impurity such as water.
Catalyzer main active component γ-FeOOH of the present invention, the surface that is dispersed in liquefaction coal is strip, and the globule size scope is long 60～200nm, wide 20～100nm, relatively Shi Yi globule size scope is long 60～150nm, wide 20～50nm.Because catalyst activity component particles size is little, thereby has very high catalytic activity, the addition of catalyst for coal liquefaction is counted 0.3～1.5% of dry coal by wherein Fe, and relatively Shi Yi addition is 0.5～1.0wt% of dry coal.
Catalyzer outward appearance of the present invention is black or Vandyke brown fine powder shape or loose bulk, is once to use the abandoning property catalyzer that need not reclaim.
Preparation of catalysts method of the present invention is, at room temperature with FeSO
4Solution joins in the carrier coal, and the carrier coal is the part of preparation coal oil mixture with coal, after stirring, adds the basic solution of hydroxyl-containing ion again, makes after continuing to stir and is loaded with Fe (OH)
2Sedimentary coal slurry.Fe (OH) will be loaded with then on the coal
2Sedimentary coal slurry is oxidized to γ-FeOOH with air or oxygen at 20～50 ℃, at last above-mentioned coal slurry is made the catalyzer finished product through filtering or filter after drying.
The present invention has the following advantages:
Catalyst activity component high dispersing is of a size of nano level on the liquefaction coal surface, is difficult for regrouping, thereby active high, consumption is few.
The catalyst prod stable in properties is easy to transportation and preservation, uses its activity unaffected after the long-term storage.
The catalyst prod raw material sources is extensive, with low cost, and the catalyzer cost that DCL/Direct coal liquefaction per ton consumed is 5～50 yuan/ton of Renminbi (liquefaction coal, a butt).
Description of drawings:
Fig. 1 be a kind of be the sample photo of the catalyzer of the present invention of preparing carriers with Chinese bituminous coal.
Fig. 2 is the photo of catalyst sample shown in Figure 1 shape characteristic under 80,000 times of scanning electronic microscope.
Fig. 3 be a kind of be the sample photo of the catalyzer of the present invention of preparing carriers with Chinese bituminous coal.
Fig. 4 is the photo of catalyst sample shown in Figure 3 shape characteristic under 80,000 times of scanning electronic microscope.
Fig. 5 be a kind of be the sample photo of the catalyzer of the present invention of preparing carriers with Chinese brown coal.
Fig. 6 is the photo of catalyst sample shown in Figure 5 shape characteristic under 40,000 times of scanning electronic microscope.
Embodiment
Embodiment 1
The cited catalyzer of this example be with a kind of Chinese bituminous coal be the preparation catalyzer carrier, be main raw material with the ferrous sulfate, the DCL/Direct coal liquefaction catalyst sample of acquisition.Concrete steps are: get 5.7 kilograms of iron vitriols, add 46.88 kilograms of tap water dissolvings, join then in 15.78 kilograms of coal dusts, stirring makes the ferrous sulfate coal slurry, and other gets 2.55kg ammoniacal liquor and joins in 34.77 kilograms of tap water.Under agitation, 2/5 of above-mentioned ammonia vol is joined in the above-mentioned ferrous sulfate coal slurry, add the back and continue to stir for 10 seconds.With above-mentioned reaction product at 40 ℃, 3m
3Centrifuging is carried out in oxidation under the/h air flow quantity after oxidizing reaction is finished, resulting filter cake is a catalyzer of the present invention.The outward appearance of this catalyzer is a black particle, sees accompanying drawing 1.Catalyst sample shown in the accompanying drawing 1 is carried out the observation discovery of shape characteristic under 80,000 times of scanning electronic microscope, the size of most of catalyst activity components about wide 40nm, is seen accompanying drawing 2 at long 150nm.Analysis to this catalyzer shows that also Fe content is 5wt% in this catalyst sample, and dry coal content 65wt%, moisture are 30wt%.
With catalyzer shown in this example and correlated pyrite catalyst, be applied on the 0.1t/d DCL/Direct coal liquefaction continuous apparatus, carry out the direct liquefaction test of this bituminous coal, use circulating solvent, temperature of reaction be in 450 ℃, pressure 19.0MPa, coal-water fluid concentration 45wt% and the reactor residence time be that the main result of gelatin liquefaction that obtains under 1.6 hours the condition is as follows:
| Catalyzer | Addition (wt%, dry coal) | Coal transformation efficiency (wt%, daf coal) | Distilled oil yield (wt%, daf coal) |
| China's charcoal kiln mouth pyrite (two sections wet-millings, mean particle size is less than 1 micron) | Raw ore=4.5% (wherein Fe=1.97) | 86.60 | 45.70 |
| Catalyzer of the present invention | Fe＝0.7 | 87.11 | 50.60 |
Embodiment 2
The cited catalyzer of this example is to be the carrier of preparation catalyzer with a kind of Chinese bituminous coal, is main raw material with the divalent iron salt, and the straight hydrogenation of a kind of coal of acquisition connects liquefaction high dispersive abandoning property ferrum-based catalyst.The outward appearance of this catalyst sample also is a black powder shape fine particle, sees accompanying drawing 3.Catalyst sample shown in the accompanying drawing 3 is carried out the observation discovery of shape characteristic under 80,000 times of scanning electronic microscope, the size of most catalyst activity component about wide 40nm, is seen accompanying drawing 4 at long 100nm.Analysis to this catalyzer shows that also Fe content is 7wt% in this catalyst sample, and dry coal content 89wt%, moisture are 4wt%.
With catalyzer shown in this example and correlated pyrite catalyst, be applied on the 0.1t/d DCL/Direct coal liquefaction continuous apparatus, carry out the direct liquefaction test of this bituminous coal, use circulating solvent, temperature of reaction be in 455 ℃, pressure 19.0MPa, coal-water fluid concentration 45wt% and the reactor residence time be that the main result of gelatin liquefaction that obtains under 2.0 hours the condition is as follows:
| Catalyzer | Addition (wt%, dry coal) | Coal transformation efficiency (wt%, daf coal) | Distilled oil yield (wt%, daf coal) |
| China's charcoal kiln mouth pyrite (two sections wet-millings, mean particle size is less than 1 micron) | Raw ore=4.5% (wherein Fe=1.97) | 90.76 | 52.79 |
| Catalyzer of the present invention | Fe＝1.0 | 91.22 | 57.17 |
Embodiment 3
The cited catalyst sample of this example be with a kind of Chinese brown coal be the preparation catalyzer carrier, be main raw material with the divalent iron salt, abandoning property of the coal Direct Hydrogenation liquefaction high dispersive ferrum-based catalyst of acquisition.The outward appearance of this catalyzer is the Powdered fine particle of Vandyke brown, sees accompanying drawing 5.Accompanying drawing 6 is that catalyzer shown in Figure 5 is carried out the photo that shape characteristic is observed under 40,000 times of scanning electronic microscope, and the result shows that the size of most catalyst activity component is at long 100nm, about wide 40nm.Analysis to this catalyst prod shows that also Fe content is 5wt%, and dry coal content 60wt%, moisture are 35wt%.
With catalyzer shown in this example and correlated pyrite catalyst, be applied on the 0.1t/d DCL/Direct coal liquefaction continuous apparatus, carry out the direct liquefaction test of these brown coal, use circulating solvent, temperature of reaction be in 445 ℃, pressure 19.0MPa, coal-water fluid concentration 45wt% and the reactor residence time be that the main result of gelatin liquefaction that obtains under 1.5 hours the condition is as follows:
| Catalyzer | Addition (wt%, dry coal) | Coal transformation efficiency (wt%, daf coal) | Distilled oil yield (wt%, daf coal) |
| China's charcoal kiln mouth pyrite (two sections wet-millings, mean particle size is less than 1 micron) | Raw ore=4.5% (wherein Fe=1.97) | 98.36 | 51.09 |
| Catalyzer of the present invention | Fe＝0.5 | 99.22 | 55.54 |
More than three examples show that all compare with the pyrite catalyst with fine grainding, it is few to have a consumption with catalyzer of the present invention, the high characteristics of gelatin liquefaction distilled oil yield that obtain.
Claims (7)
1. abandoning property of high-dispersion iron catalyzer that is used for the coal Direct Hydrogenation liquefaction, it consists of impurity such as active ingredient γ-FeOOH, carrier coal and water.
2. according to the described catalyzer of claim 1, it is characterized in that the activity of such catalysts component is γ-FeOOH, Fe content wherein is the 1～15wt% (butt) of catalyzer, carrier is a liquefaction coal itself, the content of carrier coal is the 50～90wt% (butt) of catalyzer, and all the other content in the catalyzer are impurity such as water.
3. catalyzer according to claim 1, the Fe content that it is characterized in that the activity of such catalysts composition are the 1～8wt% (butt) of catalyzer, and carrier coal content is the 60～80wt% (butt) of catalyzer, and all the other content in the catalyzer are impurity such as water.
4. according to the described catalyzer of claim 1, it is characterized in that the active ingredient γ-FeOOH in the catalyzer is evenly distributed in the surface of carrier coal, be strip, the globule size scope is long 60～200nm, wide 20～100nm.
5. catalyzer according to claim 1 is characterized in that the globule size scope of catalyst activity component γ-FeOOH is long 60～150nm, wide 20～50nm.
6. Application of Catalyst according to claim 1 is characterized in that, the addition of catalyst for coal liquefaction is counted 0.3～1.5wt% of dry coal by Fe wherein.
7. according to claim 1 or 7 described Application of Catalyst, it is characterized in that the addition of catalyst for coal liquefaction is counted 0.5～1.0wt% of dry coal by Fe wherein.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100432186C (en) * | 2007-01-04 | 2008-11-12 | 煤炭科学研究总院 | Directly hydrogenating liquifying process for mixed coal |
| CN102010741A (en) * | 2010-11-26 | 2011-04-13 | 煤炭科学研究总院 | Method for directly liquefying coals with function of maximizing utilization of liquefied residues |
| CN102154049A (en) * | 2011-03-08 | 2011-08-17 | 煤炭科学研究总院 | Method for preparing coking coal by modification by low-order nonadhesive coal |
| CN102380396A (en) * | 2010-09-03 | 2012-03-21 | 煤炭科学研究总院 | Bimetal or multi-metal high-dispersion composite coal tar hydrogenation catalyst and preparation method thereof |
| CN102732295A (en) * | 2011-04-14 | 2012-10-17 | 中国石油化工股份有限公司 | Preparation method of coal-oil slurry coprocessed by coal-oil hydrogenation, coal-oil slurry and its coprocessing method |
| CN104096563A (en) * | 2014-07-28 | 2014-10-15 | 神华集团有限责任公司 | Iron-based catalyst and preparation method thereof |
| 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 |
| CN104826662A (en) * | 2015-05-06 | 2015-08-12 | 北京中科诚毅科技发展有限公司 | Iron catalyst for slurry reactor hydrogenation, preparation, design method, and applications thereof |
| CN105363450A (en) * | 2014-09-01 | 2016-03-02 | 中科合成油技术有限公司 | Hydro-liquefied iron-based catalyst containing carbon materials and preparation method and application of hydro-liquefied iron-based catalyst |
| CN108970614A (en) * | 2018-08-01 | 2018-12-11 | 国家能源投资集团有限责任公司 | Fe-series catalyst, preparation method and application |
| CN112156785A (en) * | 2020-10-16 | 2021-01-01 | 中国神华煤制油化工有限公司 | Direct coal liquefaction catalyst, preparation method thereof and direct coal liquefaction method |
| CN112251252A (en) * | 2020-09-25 | 2021-01-22 | 中国神华煤制油化工有限公司 | Direct coal liquefaction catalyst and direct coal liquefaction method |
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2004
- 2004-11-22 CN CN 200410091152 patent/CN1778871A/en active Pending
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100432186C (en) * | 2007-01-04 | 2008-11-12 | 煤炭科学研究总院 | Directly hydrogenating liquifying process for mixed coal |
| CN102380396A (en) * | 2010-09-03 | 2012-03-21 | 煤炭科学研究总院 | Bimetal or multi-metal high-dispersion composite coal tar hydrogenation catalyst and preparation method thereof |
| CN102380396B (en) * | 2010-09-03 | 2013-04-10 | 煤炭科学研究总院 | Bimetal or multi-metal high-dispersion composite coal tar hydrogenation catalyst and preparation method thereof |
| CN102010741B (en) * | 2010-11-26 | 2013-04-10 | 煤炭科学研究总院 | Method for directly liquefying coals with function of maximizing utilization of liquefied residues |
| CN102010741A (en) * | 2010-11-26 | 2011-04-13 | 煤炭科学研究总院 | Method for directly liquefying coals with function of maximizing utilization of liquefied residues |
| CN102154049A (en) * | 2011-03-08 | 2011-08-17 | 煤炭科学研究总院 | Method for preparing coking coal by modification by low-order nonadhesive coal |
| CN102732295B (en) * | 2011-04-14 | 2015-03-18 | 中国石油化工股份有限公司 | Preparation method of coal-oil slurry coprocessed by coal-oil hydrogenation, coal-oil slurry and its coprocessing method |
| CN102732295A (en) * | 2011-04-14 | 2012-10-17 | 中国石油化工股份有限公司 | Preparation method of coal-oil slurry coprocessed by coal-oil hydrogenation, coal-oil slurry and its coprocessing method |
| CN104096563A (en) * | 2014-07-28 | 2014-10-15 | 神华集团有限责任公司 | Iron-based catalyst and preparation method thereof |
| CN105363450A (en) * | 2014-09-01 | 2016-03-02 | 中科合成油技术有限公司 | Hydro-liquefied iron-based catalyst containing carbon materials and preparation method and application of hydro-liquefied iron-based catalyst |
| 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 |
| 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 |
| CN104826662A (en) * | 2015-05-06 | 2015-08-12 | 北京中科诚毅科技发展有限公司 | Iron catalyst for slurry reactor hydrogenation, preparation, design method, and applications thereof |
| CN108970614A (en) * | 2018-08-01 | 2018-12-11 | 国家能源投资集团有限责任公司 | Fe-series catalyst, preparation method and application |
| 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 |
| CN112251252A (en) * | 2020-09-25 | 2021-01-22 | 中国神华煤制油化工有限公司 | Direct coal liquefaction catalyst and direct coal liquefaction method |
| CN112156785A (en) * | 2020-10-16 | 2021-01-01 | 中国神华煤制油化工有限公司 | Direct coal liquefaction catalyst, preparation method thereof and direct coal liquefaction method |
| CN112156785B (en) * | 2020-10-16 | 2023-03-31 | 中国神华煤制油化工有限公司 | Direct coal liquefaction catalyst, preparation method thereof and direct coal liquefaction method |
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