CN100432186C - Directly hydrogenating liquifying process for mixed coal - Google Patents
Directly hydrogenating liquifying process for mixed coal Download PDFInfo
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- CN100432186C CN100432186C CNB2007100012155A CN200710001215A CN100432186C CN 100432186 C CN100432186 C CN 100432186C CN B2007100012155 A CNB2007100012155 A CN B2007100012155A CN 200710001215 A CN200710001215 A CN 200710001215A CN 100432186 C CN100432186 C CN 100432186C
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Abstract
The direct mixed coal hydrogenating liquefaction process includes distributing nanometer level iron system catalyst with active component gamma-FeOOH homogeneously in the surface of carrier coal, mixing the carrier coal with material coal and solvent to form coal slurry, mixing with hydrogen and preheating, and direct hydrogenating liquefaction. The process has nanometer level iron system catalyst with high dispersivity and high catalytic activity, mild hydrogenating liquefaction condition, high liquefied oil yield, low cost and no environmental pollution. The new generation of direct mixed coal hydrogenating liquefaction process may be used in direct hydrogenating liquefaction of different kinds of coal.
Description
Technical field
The present invention relates to the coal chemistry manufacture field, particularly relate to directly hydrogenating liquifying process for mixed coal.
Background technology
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, is expected to reach industrialized once more condition under the feasible prerequisite of Technological Economy.In order to realize the industrialization under the direct coal liquefaction technology economically feasible prerequisite, a kind of efficient and cheap direct liquefaction catalyzer of development and utilization and processing condition thereof are very important.
Until today, in the DCL/Direct coal liquefaction technology, adopt single coal hydrogenation liquefaction under catalyst action usually at home and abroad.Catalyst system therefor is generally 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.This class Fe-series catalyst is because active component content is lower, and its granularity is many, and so catalytic effect has limitation, the transformation efficiency of gelatin liquefaction and oily yield are also lower at micron order, and catalyst levels is bigger, generally 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.But the Fe-series catalyst wide material sources are cheap, once use and need not reclaim, and discharge with coal liquefaction residue, and environment is not constituted harmful effect, are the directions of Catalysts for Direct Coal Liquefaction and development.
The size of the DCL/Direct coal liquefaction effective catalyst active ingredient of the invention that China Coal Research Institute is developed in advance can reach nano level, and in the Direct Hydrogenation liquefaction to single coal, catalytic activity is significantly improved.
Summary of the invention
The objective of the invention is to overcome the deficiency that above-mentioned prior art exists, through exploitation and the practice of contriver through for many years direct coal liquefaction technology, the method for develop that catalytic activity height of new generation, processing condition relax, gelatin liquefaction transformation efficiency and the higher mixed coal of oily yield carrying out Direct Hydrogenation liquefaction in the presence of high-efficient iron-series catalyst.
The method of mixed coal Direct Hydrogenation liquefaction provided by the invention comprises the following steps:
(1) preparation of support of the catalyst coal
In having the container of stirring, the Fe-series catalyst that will contain catalyst activity component γ-FeOOH is evenly distributed on a certain amount of any feed coal (or claiming the carrier coal) surface, making the Fe content among γ-FeOOH is carrier coal butt weight 1～15%, preferably 1～8%; Wherein Fe-series catalyst particle main component is γ-FeOOH, and iron level is 3～8 weight %, and particle shape is a long strip shape, and wide is 20～50 nanometers, and length is 60～150 nanometers.
(2) coal slurry preparation
Support of the catalyst coal, remaining (two or more) mixed coal and solvent that step (1) is obtained prepare at coal slurry and are mixed into pumpable coal slurry in the equipment, and wherein dry coal concentration is 40～60 weight %, is preferably 45～50 weight %; Fe content is 0.2～1.5 weight % of dry coal, and the part by weight that is preferably 0.5～1.0%, two kinds of coals is 30: 70 to 70: 30; Granularity is more than 0.001～0.14mm in the feed coal, and solvent is the turning oil or the initial solvent of hydrogenation liquefaction, and (using solvent before driving, as high aromatic hydrocarbons dehydrogenation crude oil, coal tar heavy duty fraction, carbolineum fraction etc.) is preferably the hydrogenation liquefaction heavy recycle stock.
(3) Direct Hydrogenation liquefaction
The coal slurry of step (2) is mixed with gas mixture, after preheating, enter and carry out the hydrogenation liquefaction reaction in the coal hydrogenation liquefying reactor, 440～480 ℃ of liquefaction reaction temperature, preferably 450～460 ℃, mixture pressure is 10～20MPa, is preferably 15～20MPa; The residence time in reactor is 0.5～2.0 hour, is preferably 1.4～2.0 hours; Hydrogen partial pressure in the gas mixture 〉=80% is preferably 80～90%; Liquefied product obtains various liquefaction oils through separating unit, coal transformation efficiency 95～99%, extraction oil productive rate 70～75%, gas yield 15～20%.
In directly hydrogenating liquifying process for mixed coal provided by the invention, described mixed coal is two or more mixed coal, is preferably the coal of two kinds of different metamorphic grade.Described coal is brown coal and part bituminous coal such as non-caking coal, weakly caking coal, long-flame coal and bottle coal etc.Because brown coal are that a kind of liquefying activity is than higher coal, the bituminous coal that metamorphic grade is lower is that the liquefaction oil yield is than higher coal, in a broad sense, coal refers to brown coal and bituminous coal, and coal comprises the various brown coal of each real estate and the bituminous coal of part low metamorphic grade specifically.Preferably use the bituminous coal of highly active brown coal and high oily yield to be carrier for catalyzer of the present invention, mate mutually, show the activity of Fe series catalysts more.Coal is mixed when using can adopt any ratio, if two kinds of coals are mixed, weight ratio is 30: 70～70: 30 usually, and concrete ratio will decide according to ature of coal and stock number.The granularity of feed coal≤100 orders, preferred 0.001～0.14mm.Described Fe-series catalyst is:
(1) the ferrum-based catalyst particle mainly consists of γ-FeOOH;
(2) catalyst particle is shaped as long strip shape, and wide is 20～50nm, and length is 60～150nm;
(3) iron content 3～8 weight % in the ferrum-based catalyst, coal 40～75 weight % also contain water;
(4) the ferrum-based catalyst particle is dispersed in coal dust surface, long-term stability.
The ferrum-based catalyst preparation method is:
(1) a certain amount of ferrous salt solution is joined in the coal dust, stir;
(2) weak caustic solution or the strong base solution with a certain amount of hydroxyl-containing ion joins in the above-mentioned coal dust, stirs, and makes to be loaded with Fe (OH)
2Sedimentary coal slurry; The pH value of reaction end is controlled at 6.0～12.0.
(3) Fe (OH) that above-mentioned steps (2) coal slurry is uploaded
2Precipitation is oxidized to γ-FeOOH with air or oxygen;
(4) step (3) coal slurry is made high dispersive iron-based DCL/Direct coal liquefaction catalyzer through centrifuging or pressure filtration.
(seeing Chinese patent ZL03153377.9 for details).
Directly hydrogenating liquifying process for mixed coal advantage provided by the invention is that Fe series catalysts altitude distribution of the present invention is nanometer particle on the raw coal surface, catalytic activity height, the liquefaction oil yield height that obtains, difficult reunion, cheap non-environmental-pollution again.
Utilize the carrier of a kind of feed coal as preparation hydrogenation liquefaction catalyzer, the hydrogenation liquefaction that carries out dissimilar feed coals more than two kinds or two kinds can reduce the severity of gelatin liquefaction, obtain than utilizing the better effect of a kind of feed coal hydrogenation liquefaction separately, can also utilize dissimilar coal resources to greatest extent, be the direct shortening liquifying method of coal of new generation.
Embodiment
The present invention further specifies the present invention with following embodiment, but protection scope of the present invention is not limited to the following example.
Embodiment 1
This example adopts the feed coal of two kinds of dissimilar Direct Hydrogenation liquefaction to carry out direct shortening liquefaction.In two kinds of feed coals, a kind of is the higher Gansu bituminous coal of liquefaction oil yield (coal A), and another kind is the higher Gansu brown coal of specific activity (coal B).With the coal B of the coal A of 35 weight % and 65 weight % feed coal as Direct Hydrogenation liquefaction, and with the carrier coal of part of coal A as preparation hydrogenation liquefaction catalyzer.γ-FeOOH is evenly distributed on part of coal A surface with hydrogenation liquefaction activity of such catalysts component.The outward appearance of the direct liquefaction raw material A after the loading catalyst active ingredient that obtains still is black particle, and the Fe content in the catalytic active component that contains among the coal A of loading catalyst is 5wt%.
With 200～460 ℃ component in the coal A of coal A, coal B and loading catalyst and the liquefaction oil is that to make dry coal concentration after the solvent be 45% coal slurry, Fe content in the hydrogenation liquefaction activity of such catalysts component that loads is 0.5% of dry coal, on the DCL/Direct coal liquefaction continuous apparatus, carry out these two kinds dissimilar mixed coal direct liquefactions of coal A and coal B, temperature of reaction be under 450 ℃, pressure 19.0MPa in reactor the residence time be 1.6 hours, the gelatin liquefaction result who obtains; The gelatin liquefaction that obtains with single coal A and single coal B under identical gelatin liquefaction condition mainly the results are shown in table 1 as a comparison:
Table 1 coal A and coal B mixed coal shortening liquefaction effect
| ％ | Transformation efficiency | The distilled oil yield | The extraction oil yield | Gas yield |
| The inventive method | 98.14 | 62.22 | 73.72 | 16.73 |
| Single coal A | 97.70 | 61.00 | 71.87 | 16.36 |
| Single coal B | 97.47 | 58.69 | 73.58 | 14.34 |
| Increased value | +0.53 | +2.03 | +1.26 | +1.08 |
Embodiment 2
This example adopts the feed coal of two kinds of dissimilar Direct Hydrogenation liquefaction to carry out direct shortening liquefaction.In two kinds of feed coals, a kind of is the higher Gansu bituminous coal of liquefier carburetion yield (coal A), and another kind is the higher brown coal of specific activity (coal C).Coal A with 50% and 50% coal C be as the feed coal of Direct Hydrogenation liquefaction, and with the carrier coal of part of coal A as preparation hydrogenation liquefaction catalyzer.γ-FeOOH is evenly distributed on part of coal A surface with hydrogenation liquefaction activity of such catalysts component.The outward appearance of the direct liquefaction raw material A after the loading catalyst active ingredient that obtains still is black particle, and the Fe content in the catalytic active component that contains among the coal A of loading catalyst is 5wt%.
With 200～460 ℃ component in the coal A of coal A, coal C and loading catalyst and the liquefaction oil is to make the coal slurry that dry coal concentration is 48 weight % after the solvent, Fe content in the hydrogenation liquefaction activity of such catalysts component that loads is 0.7% of dry coal, on the DCL/Direct coal liquefaction continuous apparatus, carry out these two kinds dissimilar mixing DCL/Direct coal liquefaction of coal A and coal C, temperature of reaction be under 450 ℃, pressure 19.0MPa in reactor the residence time be 1.0 hours, the gelatin liquefaction result who obtains; The gelatin liquefaction that obtains with single coal A and single coal C under identical gelatin liquefaction condition mainly the results are shown in table 2 as a comparison:
The effect of table 2 coal A and coal C mixed coal hydrogenation liquefaction
| ％ | Transformation efficiency | The distilled oil yield | The extraction oil yield | Gas yield |
| The inventive method | 97.72 | 60.55 | 73.63 | 15.17 |
| Single coal A | 97.47 | 58.69 | 73.58 | 14.34 |
| Single coal C | 96.19 | 58.15 | 70.27 | 15.69 |
| Increased value | +0.88 | +2.13 | 1.70 | +0.16 |
Claims (3)
1, a kind of directly hydrogenating liquifying process for mixed coal comprises the following steps:
(1) preparation of support of the catalyst coal
In having the container of stirring, the Fe-series catalyst that will contain catalyst activity component γ-FeOOH is evenly distributed on a certain amount of any raw material carrier coal surface, making the Fe content among γ-FeOOH is carrier coal butt weight 1～15%, wherein ferrum-based catalyst particle main component is γ-FeOOH, iron level is 3～8 weight %, particle is a long strip shape, and wide is 20～50 nanometers, and length is 60～150 nanometers;
(2) coal slurry preparation
Support of the catalyst coal, remaining mixed coal and solvent that step (1) is obtained are mixed into coal slurry, and wherein dry coal concentration is 40～60 weight %, and Fe content is 0.2～1.5 weight % of dry coal, and raw coal size is 0.001～0.14mm;
(3) Direct Hydrogenation liquefaction
The coal slurry of step (2) is mixed with gas mixture, after preheating, carry out Direct Hydrogenation liquefaction, 440～480 ℃ of liquefaction reaction temperature, mixture pressure is 10～20MPa, the residence time is 0.5～2.0 hour, hydrogen partial pressure in the gas mixture 〉=80%, and liquefied product obtains various liquefaction oils through separation.
2, according to the directly hydrogenating liquifying process for mixed coal of claim 1, it is characterized in that described mixed coal is two kinds, wherein a kind of is the high brown coal of liquefying activity, and another kind is the higher bituminous coal of liquefaction oil yield, and the weight ratio of brown coal and bituminous coal is 30: 70～70: 30.
3,, it is characterized in that the Fe content among described γ-FeOOH is carrier coal butt 1～8 weight % according to the directly hydrogenating liquifying process for mixed coal of claim 1; Dry coal concentration is 45～50 weight % in the described coal slurry; Iron level is 0.5～1.0 weight % in coal; The liquefaction reaction temperature is 450～460 ℃, and mixture pressure is 15～20MPa, and hydrogen partial pressure is 80～90 weight %; The residence time is 1.4～2.0 hours.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353586B (en) * | 2007-07-25 | 2012-03-21 | 汉能科技有限公司 | Coal direct liquefaction method |
| CN102233279B (en) * | 2010-04-23 | 2013-04-17 | 金军 | Direct coal hydrogenation liquefaction catalyst and direct coal hydrogenation liquefaction method |
| 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 |
| WO2012102637A1 (en) * | 2011-01-27 | 2012-08-02 | Belova Anna Grigoryevna | Method for treating carbon-containing raw material |
| CN102250654A (en) * | 2011-06-10 | 2011-11-23 | 吴庆伟 | Method for manufacturing oil from coal |
| CN102391886A (en) * | 2011-09-27 | 2012-03-28 | 长安大学 | Dry distillation and liquefying method for coal |
| CN104588109B (en) * | 2013-11-03 | 2017-01-11 | 中国石油化工股份有限公司 | Coal tar hydrogenation catalyst, and preparation method and application 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 |
| 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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| CN1579623A (en) * | 2003-08-12 | 2005-02-16 | 煤炭科学研究总院北京煤化工研究分院 | Method for preparing high dispersion iron-base catalyst for coal direct liquefication |
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