CN105709781B - A kind of DCL/Direct coal liquefaction catalyst, preparation method and application - Google Patents
A kind of DCL/Direct coal liquefaction catalyst, preparation method and application Download PDFInfo
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- CN105709781B CN105709781B CN201610043554.9A CN201610043554A CN105709781B CN 105709781 B CN105709781 B CN 105709781B CN 201610043554 A CN201610043554 A CN 201610043554A CN 105709781 B CN105709781 B CN 105709781B
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
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- C—CHEMISTRY; METALLURGY
- 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
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
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- C—CHEMISTRY; METALLURGY
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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Abstract
The present invention relates to a kind of DCL/Direct coal liquefaction catalyst, preparation method and application, the DCL/Direct coal liquefaction catalyst is sulphur iron catalyst Fe(1‑x)S, wherein x=0.09 0.17, preferably x=0.10 0.125.The coal direct liquefaction oil of high phenol content can be made using the DCL/Direct coal liquefaction catalyst.Compared with common sulphur iron catalyst：The DCL/Direct coal liquefaction catalyst does not need to carry out activation step during the reaction, so as to reduce DCL/Direct coal liquefaction reaction condition, reduce the reaction time.And the DCL/Direct coal liquefaction catalyst amount is less（0.5‑1.0wt.%）, the high conversion rate of coal（90‑95wt.%）, oily yield height（55‑65 wt.%）, phenol yield height（12‑17 wt.%）.In addition, DCL/Direct coal liquefaction catalyst of the present invention has good dispersed and very high catalytic activity, it is easy to industrial amplification production.
Description
Technical field
The present invention relates to coal chemical technologies, and in particular to a kind of DCL/Direct coal liquefaction catalyst, preparation method and application.Belong to
The DCL/Direct coal liquefaction industry in coal chemical industry.
Background technology
DCL/Direct coal liquefaction be it is a kind of convert coal into low-sulfur, low nitrogen clear gusoline technology.German in 1913
Friedrich Bergius have invented direct coal liquefaction technology, and Germany is support war during the Second World War, successively establishes 12 coals
Liquefaction plant, Oil Production ability reach 4,230,000 tons/year.Later, the states such as the U.S., Japan, Russia all developed respective characteristic coal
Direct liquefaction technique, Chinese Shenhua Group also ran a set of DCL/Direct coal liquefaction megaton device since 2008.Coal
Direct liquefaction is coal first to be worn into coal dust to be made into coal with solvent (petroleum distillate), then in high temperature, high pressure and catalyst
Under the action of directly with hydrogen occur hydrocracking reaction, coal is made to be directly translated into liquid oil, catalyst is in the direct liquid of coal
It plays an important role in change, catalyst can effectively facilitate the pyrolysis of coal and add hydrogen, improve generation oily yield and oil quality.Through
The research of last 100 years is crossed, Fe-series catalyst can be being discharged with residue without the excellent of recycling since price is low after coal liquefaction
Gesture, obtain it is more pay attention to and use, the higher cobalt of activity, molybdenum, Raney nickel due to higher price, gradually abandoned or only when
Do the use of Fe-series catalyst auxiliary agent.
The coal for being suitable for DCL/Direct coal liquefaction at present generally comprises：Bituminous coal, ub-bituminous coal, lignite etc..Usually, in above-mentioned coal
Contain 10-40 wt.%（Daf coals, it is the same below）Oxygen element.Wherein, phenolic hydroxyl group Nature comparison during DCL/Direct coal liquefaction is steady
It is fixed.Therefore containing a large amount of oxygen element in liquefaction oil product, and mainly exist in the form of phenolic hydroxyl group.Wherein, phenolic compound can
It, can also the more fine chemicals of separating-purifying production to promote oily yield by hydrogenation deoxidation.If on the contrary, a large amount of oxygen
Element is lost during DCL/Direct coal liquefaction, can cause the increase of hydrogen consumption, the decline of liquefaction oil product quality, oxygen element
Waste, ultimately increases liquefaction process cost, the value for reducing liquiefied product.However, phenolic compound in current liquefaction oil
Content be generally 5wt.% or so.
It is catalyst to influence the most important factor of DCL/Direct coal liquefaction process.It is numerous research shows that：Improving catalyst can be big
Width improves coal conversion ratio, oil（N-hexane soluble matter）Yield improves reaction condition.At present, industrialized catalyst is uniquely realized
For sulphur Fe-series catalyst.It is a large amount of research shows that：The active component of catalyst may be Fe(1-x)S, different presomas and technique item
The activity that part has codetermined catalyst is different, and finally affects the course and direct liquefaction product of DCL/Direct coal liquefaction reaction
Composition.Sulphur iron catalyst or catalyst precursor are mainly at present：FeS, FeS2, Fe(1-x)S, FeCOOH, Fe2O3Deng.
Horse wind and cloud etc.（" vulcanization of ferrum-based catalyst and its influence to DCL/Direct coal liquefaction ", horse wind and cloud etc.,《Existing coal turns
Change》（Abbreviation document 1）, the 3rd phase, 2010）Disclose Fe2O3、FeSO4, the Fe that generates after FeS vulcanizations(1-x)S is catalyst,
In the case that catalyst dosage is 3%, coal conversion ratio is also only 79.8%.
Yang Wenchun etc.（" Basic study on direct liquefaction properties of Liuhuanggou coal ", Yang Wenchun etc.,《Modern chemical industry》, the 27th
Roll up supplementary issue（2）, in November, 2007）It discloses with Fe2O3For major catalyst, simple substance S is co-catalyst.Catalyst amount is coal sample
The 5% of quality, under sulphur ditch DCL/Direct coal liquefaction optimum process condition, coal total conversion is 89.6%, and oily yield reaches
50.39%.
Therefore the main problem that current catalyst faces is：1. the activity of catalyst is relatively low, coal conversion ratio is 80% or so,
Oily yield is about 50% or so；2. phenol content is only 5% or so, this is because in DCL/Direct coal liquefaction reaction oxygen element utilization rate compared with
Low, most of oxygen element fails to be retained in oil product in the form of hydroxyl groups in coal, and oxygen element utilization rate is about 30% or so；3. it urges
Agent is unstable, and sulphur iron composition and pattern constantly change during DCL/Direct coal liquefaction.
Invention content
In order to overcome the above-mentioned deficiencies of the prior art, the present invention develops a kind of DCL/Direct coal liquefaction catalyst of high activity
Fe(1-x)S does not need to activation process, can improve coal conversion ratio, oily yield and phenol yield simultaneously.The catalyst has good
Dispersed, very high catalytic activity and stability, and dosage is less, and the conversion ratio and oily yield of coal are high, are easy to industrialization and put
Big production.Particularly, which does not need to the activation process of traditional Fe-series catalyst, so as to reduce the anti-of DCL/Direct coal liquefaction
It answers condition, reduce the reaction time.
Specifically, the present invention provides a kind of DCL/Direct coal liquefaction catalyst, and the DCL/Direct coal liquefaction catalyst is non-loading type
Or the sulphur iron catalyst Fe of support type(1-x)S, wherein x=0.09-0.17, preferably x=0.10-0.125.The sulphur iron catalyst
Crystal form is single, and property is stablized in the air under normal temperature condition.
The present invention also provides a kind of preparation methods of the DCL/Direct coal liquefaction catalyst, include the following steps：
A. under 10-30oC initial temperature, 0.1-0.2mol/L iron content aqueous solutions are slowly dropped to 0.1mol-0.2/L sulfur-bearings
It in aqueous solution, and slowly heats up while dropwise addition, in 60-90oC under 10-100 revs/min of magnetic agitation after dripping
It lower stable 100-200 minutes, is filtered, washed and dried after then standing 4-24 hours again；
B. solid step A obtained is sieved, and collects the solid powder that wherein diameter is less than 150 microns；
C. obtained solid powder in step B is placed in Muffle furnace, hydrogen or hydrogen sulfide protective gas is passed through, in 120-
It is restored 1-4 hours under 500oC；It is collected after being cooled to room temperature after having restored with above-mentioned protective gas purging, it is direct to obtain the coal
Deliquescence accelerant.
Wherein when preparing loaded catalyst, need in advance to put into carrier in Solution Containing Sulphur Ions to be pre-mixed for 24 hours, so
Step A is repeated afterwards.The carrier of wherein described support type sulphur iron catalyst is SiO2、Al2O3、ZrO2、TiO2, molecular sieve or its group
It closes.
Wherein described iron-bearing water solution is FeSO4Or FeCl2Iron content aqueous solution；The Solution Containing Sulphur Ions are Na2S or/and
H2The aqueous solution of S or/and NaHS.
The particle size range of catalyst precursor is preferably 1-150 microns wherein described in step B, and diameter is more than 150 microns
Particle needs are ground under inert gas shielding.
Wherein described hydrogen or hydrogen sulfide protective gas are inert gas and hydrogen or hydrogen sulfide 5-8 by volume:2-5
The mixed gas of mixing, wherein the inert gas is nitrogen or argon gas.
The present invention also provides a kind of coal direct liquefaction method, wherein using DCL/Direct coal liquefaction catalyst of the present invention,
The reaction condition of wherein described DCL/Direct coal liquefaction is：Temperature is 350-450oC, preferably 350-400；For hydrogen initial pressure
For 3.0-7.0MPa, preferably 3.0-5.0MPa；Reaction time is 10-60min, preferably 10-40min.The direct liquid of coal
The dosage for changing catalyst is calculated as 0.5-1.0 wt% with dry ash free basis coal.
The advantage of the invention is that：
1. the activity of DCL/Direct coal liquefaction catalyst of the present invention is strong, coal high conversion rate reaches as high as 95%；Oily yield
It is higher, up to 65%.
2. the coal direct liquefaction oil of high phenol content can be prepared using DCL/Direct coal liquefaction catalyst of the present invention,
The yield of middle phenolic compound is 16% or so, is current more than 3 times of existing common sulphur iron catalyst, it is direct to substantially increase coal
The diversity of liquiefied product and the economy of integrated artistic.
3. DCL/Direct coal liquefaction catalyst of the present invention does not need to activation process during the reaction, so as to reduce
DCL/Direct coal liquefaction reaction condition if initial hydrogen pressure is 3.0-7.0MPa, reduces the reaction time, if the reaction time is 10-
60min。
In short, heretofore described DCL/Direct coal liquefaction catalyst not only there is good dispersed and very high catalysis to live
Property, and be easy to store, property is stablized in the air under normal temperature condition；And during DCL/Direct coal liquefaction sulphur iron composition and
Pattern does not also change.It is easy to industrial amplification production, has a extensive future.
Specific embodiment
According to the method for the present invention, it is further illustrated the present invention with reference to embodiment, but the present invention is not limited to this.
Embodiment 1
A. under 10oC initial temperature, a concentration of 0.1mol/L iron content aqueous solutions of 100ml are at the uniform velocity added drop-wise under magnetic stirring
In the Solution Containing Sulphur Ions of a concentration of 0.1mol/L of 120ml, and be added dropwise while slowly heat up, after dripping continue 60 turns/
90oC is warming up under the magnetic agitation of minute and stablizes 120min at such a temperature；Then it is filtered, washed and will wash after standing 12h
Filter cake after washing dries 3h in vacuum drying chamber under the conditions of 50oC, 0.02MPa.
B. solid step A obtained is sieved, and grinds and collect the solid powder that diameter is less than 150 microns；
C. obtained solid powder in step B is placed in Muffle furnace, is passed through H containing 40v%2The nitrogen of S and mixing for hydrogen sulfide
Gas is closed, maintains the temperature under 200oC and restores 4 hours；Then after being cooled to room temperature with above-mentioned mixed gas purging solid powder
It collects, obtains the DCL/Direct coal liquefaction catalyst Fe(1-x)S, wherein x=0.09, labeled as catalyst 1A.
Embodiment 2
A. under 10oC initial temperature, a concentration of 0.1mol/L iron content aqueous solutions of 100ml are at the uniform velocity added drop-wise under magnetic stirring
In the Solution Containing Sulphur Ions of a concentration of 0.2mol/L of 100ml, the Solution Containing Sulphur Ions include the SiO being pre-mixed for 24 hours2Carrier,
And slowly heat up while dropwise addition, continue to be warming up to 90oC under 100 revs/min of magnetic agitation and in the temperature after dripping
Degree is lower to stablize 160min；Then stand be filtered, washed afterwards for 24 hours and by the filter cake after washing in vacuum drying chamber in 50oC,
Dry 3h under the conditions of 0.02MPa.
It will need to put into Solution Containing Sulphur Ions in advance, then repeatedly step A.
B. solid step A obtained is sieved, and grinds and collect the solid powder that diameter is less than 150 microns；
C. obtained solid powder in step B is placed in Muffle furnace, be passed through containing 40v%H2Nitrogen and hydrogen gaseous mixture
Body is maintained the temperature under 250oC and is restored 4 hours；Then it is collected after being cooled to room temperature with above-mentioned mixed gas purging solid powder,
Obtain support type DCL/Direct coal liquefaction catalyst Fe(1-x)S/ SiO2, wherein x=0.10, labeled as catalyst 2A.
Embodiment 3
A. under 10oC initial temperature, a concentration of 0.1mol/L iron content aqueous solutions of 100ml are at the uniform velocity added drop-wise under magnetic stirring
It in the Solution Containing Sulphur Ions of a concentration of 0.5mol/L of 50ml, and slowly heats up while dropwise addition, continues after dripping at 60 revs/min
90oC is warming up under the magnetic agitation of clock and stablizes 120min at such a temperature；Then it is filtered, washed and will wash after standing 12h
The dry 3h under the conditions of 40oC, 0.02MPa in vacuum drying chamber of filter cake afterwards.
B. solid step A obtained is sieved, and grinds and collect the solid powder that diameter is less than 150 microns；
C. obtained solid powder in step B is placed in Muffle furnace, is passed through H containing 40v%2The nitrogen of S and mixing for hydrogen sulfide
Gas is closed, maintains the temperature under 200oC and restores 4 hours；Then after being cooled to room temperature with above-mentioned mixed gas purging solid powder
It collects, obtains the DCL/Direct coal liquefaction catalyst Fe(1-x)S, wherein x=0.125, labeled as catalyst 3A.
Embodiment 4
A. under 10oC initial temperature, a concentration of 0.2mol/L iron content aqueous solutions of 100ml are at the uniform velocity added drop-wise under magnetic stirring
In the Solution Containing Sulphur Ions of a concentration of 0.4mol/L of 100ml, and be added dropwise while slowly heat up, after dripping continue 60 turns/
70oC is warming up under the magnetic agitation of minute and stablizes 120min at such a temperature；Then it is filtered, washed and will wash after standing 12h
Filter cake after washing dries 3h in vacuum drying chamber under the conditions of 40oC, 0.02MPa.
B. solid step A obtained is sieved, and grinds and collect the solid powder that diameter is less than 150 microns；
C. obtained solid powder in step B is placed in Muffle furnace, is passed through H2S gases are maintained the temperature under 150oC and are restored
4 hours；Then it is collected after being cooled to room temperature with above-mentioned mixed gas purging solid powder, obtains the DCL/Direct coal liquefaction catalyst
Fe(1-x)S, wherein x=0.17, labeled as catalyst 4A.
For convenience of contrast and experiment, ensure the reliability of conclusion, the following conditions remain unchanged：DCL/Direct coal liquefaction reactor
For 500 milliliters of autoclaves；Coal is selected from Hulun Buir lignite（Table 1）, coal diameter is no more than 150 microns；Hydrogen supply dissolvent is four
Hydrogen naphthalene.Reaction result is using dry ash free basis coal as substrate.（Table 1, to the property produced coal）
The Industrial Analysis and elemental analysis of 1 coal of table（%, ad）
| Title | Moisture | Ash content | Volatile matter | N | C | H | S | O |
| Hulun Buir lignite | 9.69 | 11.01 | 42.37 | 1.02 | 58.56 | 3.50 | 0.38 | 15.83 |
The condition of DCL/Direct coal liquefaction reaction：Reaction temperature：450oC, hydrogen first pressing：6.0MPa, reaction time 20min.It is former
Material：Coal 30g, naphthane 50g, catalyst 0.6g, elemental sulfur 0.2g.
Provided in table 2 above-mentioned preparation catalyst 1A-3A and conventional sulphur iron catalyst under the above-described reaction conditions
Coal conversion ratio, oily yield, phenol yield effect data.
The dosage and performance of 2 different catalysts of table
| Catalyst | Additive amount/% | Reaction time/h | Temperature/°C | Coalification rate/% | Oil yield/% | Phenol yield/% |
| FeS（Ore） | 1 | 1 | 450 | 72 | 43 | 3 |
| FeS（Synthesis） | 1 | 1 | 450 | 68 | 47 | 4 |
| FeS2 | 1 | 1 | 450 | 55 | 29 | 6 |
| Fe(1-x)S（Document 1） | 1 | 1 | 450 | 82 | 55 | 5 |
| Fe2O3 | 1 | 1 | 450 | 75 | 52 | 2 |
| Fe(COOH)2 | 1 | 1 | 450 | 81 | 50 | 3 |
| Catalyst 1A | 0.5 | 0.5 | 450 | 90 | 60 | 13 |
| Catalyst 2A | 0.5 | 1 | 430 | 91 | 57 | 17 |
| Catalyst 3A | 0.5 | 0.5 | 450 | 95 | 66 | 16 |
| Catalyst 4A | 1 | 1 | 450 | 90 | 55 | 12 |
In conclusion compared with existing conventional sulphur iron catalyst, DCL/Direct coal liquefaction catalyst of the present invention is in catalyst
In the case that dosage is less than conventional sulphur iron catalyst, still there is very strong activity, and coal conversion ratio is reached as high as up to more than 90%
95%；Oily yield is also higher, and up to 65%, but also obtain the phenol yield of 12-17.
Claims (10)
1. a kind of DCL/Direct coal liquefaction catalyst, the DCL/Direct coal liquefaction catalyst is non-loading type or the sulphur iron catalyst of support type
Fe(1-x)S, wherein x=0.09-0.17, the sulphur iron catalyst crystal form is single, and property is stablized in the air under normal temperature condition,
It is characterized in that：The preparation method of the DCL/Direct coal liquefaction catalyst includes the following steps：
A. under 10-30oC initial temperature, it is water-soluble that 0.1-0.2mol/L iron content aqueous solutions are slowly dropped to 0.1mol-0.2/L sulfur-bearings
In liquid, and slowly heat up while dropwise addition, it is steady under 60-90oC under 10-100 revs/min of magnetic agitation after dripping
Determine 100-200 minutes, be filtered, washed and dried after then standing 4-24 hours again；
B. solid step A obtained is sieved, and collects the solid powder that wherein diameter is less than 150 microns；
C. obtained solid powder in step B is placed in Muffle furnace, hydrogen or hydrogen sulfide protective gas is passed through, in 120-500o
It is restored 1-4 hours under C；It is collected after being cooled to room temperature after having restored with above-mentioned protective gas purging, obtains the DCL/Direct coal liquefaction
Catalyst.
2. DCL/Direct coal liquefaction catalyst according to claim 1, wherein x=0.10-0.125.
3. DCL/Direct coal liquefaction catalyst according to claim 1 or 2, wherein the carrier of the support type sulphur iron catalyst is
SiO2、Al2O3、ZrO2、TiO2, molecular sieve or combination.
4. according to the preparation method of any one of the claim 1-3 DCL/Direct coal liquefaction catalyst, include the following steps：
A. under 10-30oC initial temperature, it is water-soluble that 0.1-0.2mol/L iron content aqueous solutions are slowly dropped to 0.1mol-0.2/L sulfur-bearings
In liquid, and slowly heat up while dropwise addition, it is steady under 60-90oC under 10-100 revs/min of magnetic agitation after dripping
Determine 100-200 minutes, be filtered, washed and dried after then standing 4-24 hours again；
B. solid step A obtained is sieved, and collects the solid powder that wherein diameter is less than 150 microns；
C. obtained solid powder in step B is placed in Muffle furnace, hydrogen or hydrogen sulfide protective gas is passed through, in 120-500o
It is restored 1-4 hours under C；It is collected after being cooled to room temperature after having restored with above-mentioned protective gas purging, obtains the DCL/Direct coal liquefaction
Catalyst.
5. preparation method according to claim 4 wherein when preparing loaded catalyst, needs in advance to put into carrier to contain
It is pre-mixed in sulphur aqueous solution for 24 hours, then repeatedly step A.
6. preparation method according to claim 4 or 5, the iron content aqueous solution is FeSO4Or FeCl2Iron content aqueous solution；
The Solution Containing Sulphur Ions are Na2S or/and H2The aqueous solution of S or/and NaHS.
7. preparation method according to claim 4 or 5, wherein the hydrogen or hydrogen sulfide protective gas are inert gas
With hydrogen or hydrogen sulfide 5-8 by volume:The mixed gas of 2-5 mixing, wherein the inert gas is nitrogen or argon gas.
8. a kind of coal direct liquefaction method, wherein using claim 1-3 any one of them DCL/Direct coal liquefaction catalyst, wherein
The reaction condition of the DCL/Direct coal liquefaction is：Temperature is 350-450oC；It is 3.0-7.0MPa for hydrogen initial pressure；Reaction
Time is 10-60min.
9. coal direct liquefaction method according to claim 8, wherein the reaction condition of the DCL/Direct coal liquefaction is：Temperature is
350-400ºC；It is 3.0-5.0MPa for hydrogen initial pressure；Reaction time is 10-40min.
10. coal direct liquefaction method according to claim 8 or claim 9, wherein the dosage of the DCL/Direct coal liquefaction catalyst with
Dry ash free basis coal is calculated as 0.5-1.0wt%.
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| CN104445440A (en) * | 2014-11-10 | 2015-03-25 | 西北师范大学 | Preparation method of Fe1-XS nanomaterial with controllable size and shape |
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