CN1145685C - Process for coal liquefaction - Google Patents
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- CN1145685C CN1145685C CNB001352377A CN00135237A CN1145685C CN 1145685 C CN1145685 C CN 1145685C CN B001352377 A CNB001352377 A CN B001352377A CN 00135237 A CN00135237 A CN 00135237A CN 1145685 C CN1145685 C CN 1145685C
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Abstract
To provide a method for liquefying coal, having a high catalytic activity, capable of improving an oil content yield in comparison with conventional methods for liquefying coal. SOLUTION: In this method for liquefying coal comprising a hydrogenation process for using an iron ore having <=10 &mu m average particle diameter mechanically ground in a coal liquefaction solvent and hydrogenating coal in the presence of a solvent, a catalyst and sulfur and/or a sulfur compound, the method for liquefying coal is characterized in that limonite having >=40 mass % iron content, 0.2-2.5 mass % Ni content, 6-20 mass % Al(OH)3 content and <=1.4 mass % Cr content is used as the iron ore useful as the catalyst.
Description
Technical field
The invention belongs to the technical field relevant with method of liquefying coal, detailed says, the technical field that belongs to relevant method of liquefying coal, this method contains the hydrogenation operation that makes coal hydrogenation in the presence of catalyzer, the technical field that particularly belongs to relevant method of liquefying coal, this method of liquefying coal are used for from coal preparation transportation liquid fuel.
Background technology
Based on energy scenario in recent years, wished strongly that exploitation substitutes the liquid fuel of oil.Particularly, because the reserve of coal is abundant, establishment has become important problem to the technology that the coal efficient liquefaction obtains liquid fuel.Various method of liquefying coal have always been proposed for this reason, typical method of liquefying coal drying with chippy coal becomes the muddy mixture with solvent after under High Temperature High Pressure feeding hydrogen liquefy with the generation hydrogenation reaction.
When making the hydrogenation reaction (liquefaction reaction) that relevant coal takes place, kind with feed coal, sometimes the catalyst component that does not add catalyzer and utilize in the coal to be contained, but general in order to improve the efficient of hydrogenation reaction, what adopt is, in described muddy mixture, add catalyzer, it is provided in hydrogenation reaction, under catalyzer and solvent coexistence, make the method for coal hydrogenation.
As catalyzer for this hydrogenation reaction efficient of raising, promptly promote the anti-catalyst for application of gelatin liquefaction (to call the gelatin liquefaction catalyzer in the following text), known various molybdenum series catalysts or the catalyzer such as zinc chloride, tin chloride or iron sulphide, ferric sulfate, ferric oxide, ironic hydroxide, red soil, iron ore that has always, but these catalyzer are not very sufficient as gelatin liquefaction with catalyzer, and various problems are arranged.
Promptly, as catalyst for coal liquefaction, except must have primary activity as catalyzer (promptly as catalyzer will improve on the such catalysis of hydrogenation reaction efficient superior), from the economic point of view of gelatin liquefaction, also must be cheaply, obtain easily, in conveying liquified coal, do not break down etc.In aforementioned catalyzer, molybdenum series catalyst also has a resource problem except price is high; Chloride catalysts such as zinc chloride then have the etching problem that causes equipment easily.Also have, though catalyzer low prices such as iron sulphide, ferric sulfate, ferric oxide, ironic hydroxide, red soil, iron ore exist as the not enough problem of activity of such catalysts (to call catalytic activity in the following text).
In these catalyzer, though the catalytic activity of iron ore is not enough because it have cheaply, than the advantage that is easier to and obtains in a large number, so be present as high a kind of of gelatin liquefaction usefulness catalyzer practicality.For this reason, for improving iron ore as the gelatin liquefaction activity of such catalysts, proposed many schemes, the inventor etc. have also proposed to have method of liquefying coal (the special flat 6-1948 of hope of following feature; Te Kaiping 7-207274): the pulverizing iron ore in coal liquefaction solvent (gelatin liquefaction circulating solvent) below the median size 10 μ m of use mechanical disintegration is as catalyzer.The advantage of described method is: the aggegation of the catalyst particle in solvent is difficult to take place, and therefore the excellent dispersion of catalyzer can improve the contact efficiency of catalyzer and coal, therefore, improve catalytic activity, reduced under the catalyst levels, made the yield of oil content improve.
Also have, the inventor etc.s are based on knowledge as described below, have proposed the raising catalytic activity and increase the method for liquefying coal of oil content yield.
That is, such fact is arranged as making catalyzer that highly active important factor be arranged, the spike of expressing catalytic activity exists under 250 ℃ of also low temperature of pyrolysated beginning than coal.The chemical form of the spike of iron cpds such as iron ore all is to be referred to as pyrrhotite (Pyrrhotite, Fe
1-xS) iron sulphide a kind of, the temperature that changes to pyrrhotite than 250 ℃ of also high situations under, to not having abundant hydrogen supply at the thermolysis free radical that so far takes place between the transition temperature from 250 ℃, generated many undesirable polycondensates, make the yield of oil content descend.In view of the above, wish that iron cpd will be below 250 ℃ to the transition temperature of pyrrhotite.
Pyrrhotite (Fe
1-xS) katalysis and its level of activity and iron cpd are all different with the kind of iron cpd to the transition temperature of pyrrhotite, and particularly alkali formula ironic hydroxide (FeOOH) is curing below 250 ℃, change to pyrrhotite, demonstrate high catalytic activity.
The inventor etc. based on such knowledge, have proposed to have method of liquefying coal (the special flat 10-32876 of hope of following feature; Te Kaiping 11-228972) with the mol ratio of inherent moisture and iron atom more than 0.4, the limonite of oxygen-free iron is as catalyzer in fact.The advantage of described method is, FeOOH in the catalyzer cures at the low temperature below 250 ℃ and changes to the pyrrhotite as spike, for this reason, carry out sufficient hydrogen supply for the thermolysis free radical that thermolysis produced by coal, suppressed the generation of undesirable polycondensate, therefore, the yield of oil content is improved.
Yet, consider from the economy of liquidation of coal, aforementioned can't saying so fully of having proposed with iron ore catalyzer such as pulverizing iron ore catalyzer, limonite catalyzer, and, also have irregular as activity of such catalysts with the place of production of iron ore, mining area etc., for from being economically advantageous to the carrying out of liquidation of coal reaction, develop high catalytic activity more and coal liquefaction method that the oil content yield is increased with regard to hope.
Summary of the invention
The present invention is conceived to these situations and does, and its objective is to provide with coal liquefaction method always to compare, and higher catalytic activity is arranged so that the coal liquefaction method that the oil content yield increases.
For achieving the above object, the coal liquefaction method relevant with the present invention has 1～7 described coal liquefaction method of invention, and this method has following formation.Promptly, invent 1 described coal liquefaction method, contain the hydrogenation operation, described hydrogenation operation is: in coal liquefaction solvent, use the median size of mechanical disintegration: the iron ore below the 10 μ m is as catalyzer, in the presence of solvent and catalyzer and sulphur and/or sulfide, to coal hydrogenation, it is characterized in that: the iron ore that uses as described catalyzer is to use iron level: 40 quality % are above, Ni content: 0.2～2.5 quality %, Al (OH)
3Content: 6～20 quality %, Cr content: the limonite (the 1st invention) that 1.4 quality % are following.
Inventing 2 described coal liquefaction methods is according to invention 1 described method of liquefying coal, it is characterized in that: the iron in the described limonite contains (the 2nd invention) as the iron cpd that contains alpha-feooh.Inventing 3 described coal liquefaction methods is to it is characterized in that according to invention 2 described method of liquefying coal: described iron cpd is the iron cpd (the 3rd invention) that is substantially free of ferric oxide.
Inventing 4 described coal liquefaction methods is to it is characterized in that according to invention 1,2 and 3 described method of liquefying coal: the Ni in the described limonite is as containing NiFe
2O
4Nickel compound contain (the 4th invention).Inventing 5 described coal liquefaction methods is to it is characterized in that according to invention 1,2,3 and 4 described method of liquefying coal: the nickel in the described limonite is as NiFe
2O
4Contain (the 5th invention).
Invent 6 described coal liquefaction methods and be according to invention 1,2,3,4 and 5 described method of liquefying coal and it is characterized in that: the amount of described sulphur and/or sulphur compound is 1.0～5.0 (the 6th invents) by the atomic ratio of wherein sulfur content and the iron amount in the described limonite.Inventing 7 described coal liquefaction methods is according to invention 1,2,3,4,5 and 6 described method of liquefying coal, it is characterized in that: use the solid Sulfur as described sulphur (the 7th invention).
Embodiment
The present invention implements like that by for example following.
With break-up of catalyst such as ball mill machine, in coal liquefaction solvent, more than the iron level 40 quality %, nickel content 0.2～2.5 quality %, Al (OH)
3The following limonite mechanical disintegration of content 6～20 quality %, chromium content 1.4 quality % becomes below the median size 10 μ m.Then, in coal, add solvent, add the above-mentioned limonite of having pulverized again, add sulphur again, obtained the muddy mixture as promotor as catalyzer.Next, under High Temperature High Pressure, make coal hydrogenation to the logical hydrogen of this muddy mixture.
Under such form, implement the relevant coal liquefaction method of the present invention.
Action effect of the present invention mainly is described below.
Limonite (Limonite) is generated by basic rock weathering under the weather that high temperature wets more, particularly, in Indonesia, is accompanied by in the top section digging nickel ores from nickel ore deposit, will give off about 10,000,000 tons of such limonite every year.This limonite is except the iron that contains 30～60 quality %, the Al (OH) of 3～30 quality %
3, 0.1～2.5 quality % nickel outside, metal ingredients such as also siliceous and small additions of chromium, cobalt.Because such ore iron branch is many, nickel content is low, so limonite is not evaluated as nickel minerals, marked down and a large amount of obtains.
When using described limonite to use catalyzer as gelatin liquefaction, with its median size below 10 μ m for well.When median size surpassed 10 μ m, surface availability of catalyst long-pending (outer surface area of the catalyst particle of per unit catalyst quality) was little and make the contact efficiency of catalyzer and coal low, can not get the catalytic activity of being expected.Such surface availability of catalyst is long-pending in order to increase, the raising catalytic activity, and median size, is wished below 5 μ m from described viewpoint with the smaller the better below 10 μ m.
Particularly, when the regulation catalyzer median size when 5 μ m are following, from industry, carry out favourable than dry type in coal liquefaction solvent, to carry out mechanical disintegration.Compare with pulverizing with the dry type of jet mill etc., in coal liquefaction solvent, carry out to come far for effectively with medium stirring-type pulverizer etc., simultaneously, in containing the muddy mixture of coal, solvent and catalyzer, pulverize the catalyzer that obtains by dry type and in solvent, have the agglutinative tendency, and in coal liquefaction solvent, pulverize catalyzer good dispersity in solvent of gained, the effect that improves catalytic activity is arranged.Also have, the occasion that the median size of catalyzer fixes on 5～10 μ m also has such effect.
The inventor etc. as the gelatin liquefaction catalyzer, carry out the gelatin liquefaction reaction to various limonites mechanical disintegration in coal liquefaction solvent to them, to estimate its catalytic activity to median size 10 μ m.Can know by the result, with more than the iron level 40 quality %, nickel content 0.2～2.5 quality %, Al (OH)
3The occasion of the limonite of content 6～20 quality %, chromium content 1.4 quality % following (containing 0 quality %), its catalytic activity height.
Based on above-mentioned knowledge, the coal liquefaction method relevant with the present invention contains the hydrogenation operation, this hydrogenation operation be to use in coal liquefaction solvent mechanical disintegration, the iron ore below the median size 10 μ m is as catalyzer, make in the presence of solvent and catalyzer and sulphur and/or the sulfide coal hydrogenation it is characterized in that the iron ore that uses as described catalyzer be with iron level 40 quality % more than, nickel content 0.2～2.5 quality %, aluminium hydroxide content 6～20 quality %, limonite (the 1st invention) below the chromium content 1.4 quality %.As according to described coal liquefaction method, by above-mentioned knowledge as can be known, because its catalytic activity improves, so the oil content yield can increase. for this reason, just might under the adding little amount of catalyst, obtain high oil content yield.Thus, be more conducive to liquidation of coal economically.Also have, above-mentioned chromium content is being meant below the 1.4 quality % that chromium more than the 0 quality %, below the 1.4 quality %, also comprises the situation that does not contain chromium.
In the coal liquefaction method relevant with the present invention, the catalyzer of usefulness is limited to and consists of iron level 40 quality % above, nickel content 0.2～2.5 quality %, Al (OH)
3The limonite that content 6～20 quality %, chromium content 1.4 quality % are following so limit such composition, describes its reason in detail below.
In the coal liquefaction method relevant with the present invention, the catalyzer limonite uses in the presence of sulphur and/or sulphur compound, and the iron cpd in the limonite is transformed into as a kind of pyrrhotite (Fe in the iron sulphide
1-xS), give expression to high catalytic activity.For this reason, the iron level in limonite is high more, and the activity of per unit catalyst quality also uprises; During iron level less than 40 quality %, few as the pyrrhotite quantitative change of spike, catalytic activity is descended, just must be with many catalyst levelss for obtaining desired catalytic activity, this has just produced the problem of catalyzer cost up.Therefore, the iron level in the limonite is necessary more than 40 quality %.
Nickel in the limonite has the active effect of demonstration as catalyzer to the hydrogenation of the aromatics in the coal., be advisable with the many persons of nickel amount, but when the nickel amount surpassed the situation of 2.5 quality %, with respect to the increase of nickel amount ratio, the degree that catalytic activity increases was little, and cost becomes higher, so economy descends as catalytic activity for this reason.On the other hand, during nickel quantity not sufficient 0.2 quality %, just can not get abundant effect as above-mentioned catalyst action.Therefore, nickel content is limited to 0.2～2.5 quality % in the limonite.
Al in the limonite (OH)
3100～300 ℃ of heating change is Al
2O
3, the effect of demonstration as weakly acidic catalytic activity arranged, also have, with alkali formula ironic hydroxide (FeOOH) interaction in the limonite, played the aggegation that suppresses as the pyrrhotite of spike, the effect that improves catalytic activity.But, at Al (OH)
3During quantity not sufficient 6 quality %, above-mentioned effect just can not get effect of sufficient.On the other hand, at Al (OH)
3When amount surpassed 20 quality %, can't see above-mentioned effect had tangible increase, had produced the problem that diminishes catalytic activity is reduced because of iron level on the contrary.Therefore, Al (OH) in the limonite
3Amount is limited to 6～20 quality %.
Also has the Al during heating in the limonite (OH)
3Generated atomic thin Al
2O
3Particle (particulate), this Al
2O
3Aforesaid excellent catalytic activity action effect is also arranged.In contrast, the aluminium in limonite is at first with Al
2O
3When state exists, this Al
2O
3Even heat the also constant particulate that becomes, its catalytic activity is low, can not get aforesaid excellent catalytic activity action effect, so effect is not enough.In view of the above, the Al in the limonite must be from from the beginning of just with Al (OH)
3Form be contained in the limonite, its amount is 6-20 quality %.
Chromium has in the hydrocarbon compound dehydrogenation reaction and shows active function as catalyzer.For this reason, when chromium content surpasses 1.4 quality %, when hindering the coal hydrogenation reaction, also can produce such problem, make hydrogenant product dehydrogenation once again and change undesirable polycondensate, reduction oil content yield into.In view of the above, chromium content is necessary below 1.4 quality %, and the least possible person is preferred, particularly, because the katalysis of chromium amount its dehydrogenation reaction when 0.5 quality % is following sharply descends, so wish the chromium amount below 0.5 quality %, wherein 0 quality % (not containing chromium) person is for the most satisfactory.
Use the powder X-ray diffraction analysis, conclude that limonite generally is alpha-feooh and α-Fe
2O
3, but, with the place of production, mining area difference, alpha-feooh and α-Fe
2O
3The component proportions difference, the content of alpha-feooh (α-alkali formula ironic hydroxide) is many more, the temperature that changes to pyrrhotite is low more, catalytic activity uprises.
From described point, the iron in the limonite of wishing to use as catalyzer contains (the 2nd invention) as the iron cpd that contains alpha-feooh.In the case, the thermolysis free radical that the thermolysis by coal is produced has carried out abundant hydrogen supply, has suppressed the generation of undesirable polycondensate, thereby has just obtained the increase of oil content yield with few catalyst levels.
Furtherly, wish that above-mentioned iron cpd is all (except NiFe
2O
4Deng composite oxides in iron cpd outside whole) be alpha-feooh, promptly above-mentioned iron cpd is to be substantially free of ferric oxide (to remove NiFe
2O
4Deng composite oxides in iron cpd beyond) iron cpd (the 3rd invention).In this occasion, more reliably to above-mentioned thermolysis free radical carry out abundant hydrogen supply, suppress polycondensate generation, just can make the increase of oil content yield with few catalyst levels.
Nickel content in the limonite is defined in 0.2～2.5 quality % as previously mentioned.In order to make a spot of like this nickel content can produce the catalytic effect of maximum nickel, wish that nickel is present near the pyrrhotite as spike.
From described point, wish that the nickel in the limonite is as containing NiFe
2O
4Nickel compound and contain (the 4th invention).In this occasion, by the interaction of pyrrhotite and nickel catalytic activity is improved, therefore, just can improve the oil content yield with few catalyst levels.That is, because above-mentioned NiFe
2O
4It is the represented oxide compound (composite oxides of iron and nickel) of form of having been replaced by nickel with a part of iron of the oxide compound of iron, when curing, the part of the oxide compound of wherein iron or iron is transformed into pyrrhotite, nickel just be present in the utmost point be close to this pyrrhotite near, in view of the above, the interaction of pyrrhotite and nickel is increased catalytic activity thus, with a spot of catalyst levels the yield of oil content is improved.
And then, wish that nickel in the limonite is as NiFe
2O
4And contain it (5th invention).In this occasion, the interaction by pyrrhotite and nickel improves catalytic activity more reliably, therefore, uses few catalyst levels just can improve the oil content yield.
Among the present invention, the iron in the limonite cures and becomes pyrrhotite, has played as the effect of gelatin liquefaction with catalyzer, therefore wishes to be sulfided into pyrrhotite when the hydrogenation reaction of coal.This sulfuration sulphur and/carry out in the presence of the sulphur compound, sulfuration for this reason, sulphur with/sulphur compound is necessary.Sulphur in the feed coal and/or content of sulphur compounds after a little while, wish to add sulphur and/sulphur compound so that the iron in the limonite by tight cure.
From described point, wish sulphur and/amount of sulphur compound is better (6th invent) at 1.0 the above atomic ratio 1.0～5.0 by the atomic ratio (S/Fe atomic ratio) of wherein sulfur content and the iron amount in the described limonite.In the case, the iron in the limonite changes pyrrhotite fully into, therefore, can improve the yield of oil content under with few catalyst levels situation.When sulphur and/amount of sulphur compound is lower than 1.0 occasion by the S/Fe atomic ratio, the iron in the limonite does not fully change pyrrhotite into, catalytic activity reduces.On the other hand, though add volume sulphur and/sulphur compound makes the S/Fe atomic ratio surpass at 5.0 o'clock, increase effect that also can't see aforesaid oil content yield is significantly improved, instead the cost recovery of sulphur and/or sulphur compound has been improved.
The occasion that adds sulphur can use the solid Sulfur to be used as described sulphur (the 7th invention).
As coal, can use outside the low degree of carbonisation coals (coal that degree of carbonisation is low) such as brown coal, can also use sub-bituminous coal and bituminous coal.These normally are ground into after below 15% than about 60 orders thinner granularities at drying to moisture and use, and do the carrying out that can help gelatin liquefaction like this, but are not limited to do like this.
The not special restriction of hydrogenation conditions in the hydrogenation operation, so long as the condition that causes hydrogenation reaction just, usually under the hydrogen dividing potential drop of 350～500 ℃ temperature, 7～20MPa and reaction times 10～120min condition, carry out, do the carrying out that can help gelatin liquefaction like this.Also can be after solids components such as separating liquiding catalyst, reclaiming as oil content by the resulting hydrogenation products of hydrogenation reaction, normally the oil content of described after separating is sent into distillation tower and separate, reclaim desired object (heavy oil, middle oil, light oil etc.), meanwhile, the part of this heavy oil etc. is used as circulating solvent and recycles in the mud preparation process.
Coal liquefaction solvent also is referred to as the gelatin liquefaction circulating solvent, so-called coal liquefaction solvent (gelatin liquefaction circulating solvent) is meant the first gelatin liquefaction circulating solvent and the second gelatin liquefaction circulating solvent etc., this first gelatin liquefaction circulating solvent is: (obtain coal in preparation mud operation, the operation of the slurry mixture of solvent and catalyzer coexistence) uses as solvent in, thereafter, separated from solvent operation or separating of oil operation (by from separation such as hydrogenation products distillation operation and with the operation of separated from solvent and with oil content isolating operation) be separated in the product (hydrogenation products) from the hydrogenation operation of coal (make cause hydrogenation reaction and with the operation of gelatin liquefaction) as solvent being, use as being recycled the solvent of supplying with preparation mud operation, carry out these operations later on repeatedly, round-robin solvent between preparation mud operation and separated from solvent operation or oil content separation circuit; This second gelatin liquefaction circulating solvent is: as solvent and separated, as required, circulation is supplied with and is removed the solvent of preparing the operation the mud operation in above-mentioned separated from solvent operation or separating of oil operation.
Coal liquefaction solvent supplies with as circulation nearly all that solvent in the mud preparation process uses, but in the present invention, and the part of this coal liquefaction solvent is imported the machine that crushing catalyst uses and is used for pulverizing therein limonite.That is, institutes such as above-mentioned separated from solvent operation or oil content separation circuit are separated the solvent that obtains and supply with the mud preparation process as coal liquefaction solvent on the one hand; Pulverize the pulverizer that limonite is used therein and on the other hand the part in this solvent is supplied with.
Embodiment
Embodiments of the invention are described below, but only otherwise exceed aim of the present invention, the present invention is not limited to these embodiment.Also has the value that coal transformation efficiency described in the following examples, the comparative example, yield value all are is benchmark with anhydrous ashless carbon.
The limonite that embodiment, comparative example are used (A～F)
Get limonite A～F that Indonesia produces, by after Jiyu mill (nara machinery the is made made) coarse reduction, drying under reduced pressure is standby after 8 hours under 110 ℃ of temperature respectively.
Table 1 shows the metal analysis value in the above-mentioned limonite and the result of powder X-ray line diffraction analysis (XRD analysis).Wherein, metal analysis value the limonite sample with after the aqueous hydrochloric acid heating for dissolving by the quantitative assay of atom light absorption method.Powder X-ray line diffraction analysis is to carry out under acceleration voltage 40kV, 200mA with X-ray diffraction device (the PINT1500 type that motor of science company makes), identifies the iron in the limonite and the form of nickel and aluminium simultaneously.
The result who is analyzed by X-ray diffraction detects in all limonites (limonite A, B, C, D, E and F) and is equivalent to alpha-feooh and Al (OH) as can be known
3The peak.In these limonites, among limonite B, C, E and the F, except detecting alpha-feooh, also detect and be equivalent to NiFe
2O
4The peak.In limonite A, except detecting alpha-feooh, also detect and be equivalent to α-Fe
2O
3The peak.In limonite A and D, do not detect and be equivalent to NiFe
2O
4The peak.
In the occasion of all limonites, the aluminium in the limonite is entirely with Al (OH)
3Form contain and do not detect Al
2O
3The peak.
When obtaining by the Al shown in the table 1 (OH)
3The Al that amount is converted into
2O
3Value [Al (OH)
3Heating change becomes Al
2O
3The time Al
2O
3Amount] and SiO
2The ratio of amount, i.e. Al
2O
3/ SiO
2The time, limonite A is 4.2, and limonite B is 6.9, and limonite C is 3.3, and limonite D is 2.0, and limonite E is 3.0, and limonite F is 1.2.
Embodiment 1
Above-mentioned limonite A is pulverized in coal liquefaction solvent (brown coal liquefaction solvent) with P-5 type planet pulverizer (manufacturing of Fu Liqiu company), obtain catalyzer mud.At this moment, be made as the ball of pulverizing usefulness by the SUS316 of diameter 10mm.The specific surface area of the limonite after the pulverizing is 40.2m
2/ g.In addition, during the size-grade distribution of the limonite when measure above-mentioned catalyzer mud with laser diffractometry in, its median size is 0.8 μ m.
Then, the class that above-mentioned catalyzer mud is joined Indonesia's product kowtows in the brown coal, adds sulphur simultaneously, adds the brown coal liquefaction solvent again, obtains the muddy mixture.At this moment, be benchmark in the moisture ash free coal, the add-on of catalyzer is 1.0 quality % of iron, and is to be benchmark in the moisture ash free coal, the add-on of sulphur is the 1.2 quality % (S/Fe atomic ratio 2.0) of iron.
Above-mentioned muddy compound is imported autoclave (internal volume is 100mL), under the reaction conditions of hydrogen first pressing 10MPa, 450 ℃ of temperature of reaction and reaction times 30min, carry out hydrogenation reaction (liquefaction reaction).Then, separating obtained reaction product (hydrogenation products) makes the reaction product dissolving with tetrahydrofuran (THF) (THF) and normal hexane, with the film filter filtering separation of fine pore 0.2 μ m.The solid phase composition that filtering separation is thus obtained, be that the insoluble composition of THF (undissolved composition in THF) is defined as the unreacted brown coal, brown coal amount before unreacted brown coal amount and the hydrogenation reaction is obtained the brown coal amount of having reacted thus, has just obtained coal transformation efficiency (ratio of the reaction brown coal amounts brown coal amount before to hydrogenation reaction) thus.Also having, is benchmark in the moisture ash free coal, is obtained the yield of the composition that is dissolvable in water normal hexane by following formula.The results are shown in table 2.
Dissolve in the brown coal amount of the yield (quality %)=100 of the composition of normal hexane * [(the brown coal amount of adding+used up hydrogen amount)-be insoluble to the one-tenth component of hexane]/add
Embodiment 2
Replace limonite A with limonite B.Except this point, carry out liquefaction reaction with method similarly to Example 1, the yield that uses the same method and obtain the coal transformation efficiency and dissolve in the composition of normal hexane.The results are shown in table 2.
Embodiment 3
Replace limonite A with limonite C.Except this point, carry out liquefaction reaction with method similarly to Example 1, obtain coal transformation efficiency and the yield that dissolves in the composition of normal hexane.The results are shown in table 2.
Comparative example 1
Replace limonite A with limonite D, E or F.Except this point, carry out liquefaction reaction with method similarly to Example 1, obtain coal transformation efficiency and the yield that dissolves in the composition of normal hexane.The result concludes and is shown in table 2.
Embodiment 4
Above-mentioned limonite B is pulverized in the brown coal liquefaction solvent with P-5 type planet pulverizer (manufacturing of Fu Liqiu company), obtain catalyzer mud.At this moment, be 10mm as the ball of pulverizing usefulness by SUS316 system, diameter.The specific surface area of the limonite after the pulverizing is 44.5m
2/ g.Also have, the median size of the limonite in the described catalyzer mud is 0.8 μ m.
Then, the class that above-mentioned catalyzer mud is joined Indonesia's product kowtows in the brown coal, adds the solid Sulfur simultaneously, adds the brown coal liquefaction solvent again, obtains the muddy mixture.At this moment, be benchmark in the moisture ash free coal, the add-on of catalyzer is 1.0 quality % of iron, and is benchmark in the moisture ash free coal, solid sulfury add-on is the 1.2 quality % (S/Fe atomic ratio 2.0) of iron.
Above-mentioned muddy compound is imported autoclave (internal volume is 3L), under the reaction conditions of hydrogen first pressing 12MPa, 450 ℃ of temperature of reaction and reaction times 120min, carry out hydrogenation reaction (liquefaction reaction).Then, separating obtained reaction product (hydrogenation products) its distillation, is separated oil content according to each boiling spread, obtains liquefaction oil (C
5The liquid distillate that～boiling point is 420 ℃) yield.Also have,, obtain the yield of gaseous constituent with the gas in the gas chromatographic analysis autoclave.And then, the composition that is insoluble to THF in the distillation residue is defined as unconverted coal, obtain the coal transformation efficiency.The results are shown in table 3.
Embodiment 5
Solid sulfury add-on replaces S/Fe atomic ratio 2.0 with S/Fe atomic ratio 0.5.Except this point, use with the same method of embodiment 4 carry out liquefaction reaction, the yield of obtaining liquefaction oil, the yield and the coal transformation efficiency of gaseous constituent use the same method.The results are shown in table 3.
By above embodiment and comparative example, can know following each point.With the condition that satisfies the relevant limonite of the present invention (iron level more than the 40 quality %, nickel content 0.2～2.5 quality %, aluminium hydroxide content at 6～20 quality %, chromium content below 1.4 quality %) limonite A, B, C as gelatin liquefaction with having more than a kind unappeasable limonite D, E, F comparative example 1 compare in the embodiment 1,2,3 of catalyzer and the condition with the above-mentioned limonite relevant with the present invention, the former coal transformation efficiency and dissolve in yield height, liquefaction reaction activity (brown coal being converted into the ability of the oil content) excellence of the composition of normal hexane.
That is, by comparative example 1 as can be known, the limonite of being discontented with 0.2 quality % with nickel content is the occasion (limonite D) of catalyzer, and liquefying activity is low.Also have, though use nickel content Al (OH) more than 0.2 quality %
3The limonite of the discontented 6 quality % of content is the occasion (limonite F) of catalyzer and the occasion (limonite E) that chromium content surpasses 1.4 quality %, and the liquefaction reaction activity is step-down all.
Can know that with the comparison of embodiment 2 iron in the limonite is the limonite that contains and be substantially free of ferric oxide as alpha-feooh by embodiment 1, its catalytic activity height, the Ni in the limonite is as NiFe
2O
4And the person of containing is more satisfactory.
By embodiment 4 and embodiment 5 more as can be known, when the S/Fe atomic ratio of solid sulfury add-on being defined as 2.0 embodiment 4 and S/Fe atomic ratio and being 0.5 embodiment 5 and comparing, oil content (C in liquefaction reaction
5The cut that～boiling point is 420 ℃) yield height, and the yield of gaseous constituent is low, catalytic activity height, liquefaction reaction superior activity.
[table 1]
| The symbol of limonite | Composition (quality %) | XRD analysis result | ||||
| T-Fe | Ni | Al(OH) 3 | Cr | SiO 2 | ||
| A | 48.8 | 0.85 | 15.8 | 1.03 | 2.43 | α-FeOOH，α-Fe 2O 3 |
| B | 45.5 | 1.33 | 17.5 | 1.15 | 1.67 | α-FeOOH，NiFe 2O 4 |
| C | 52.5 | 0.25 | 9.2 | 0.66 | 1.84 | α-FeOOH，NiFe 2O 4 |
| D | 48.2 | 0.12 | 10.1 | 1.21 | 3.27 | α-FeOOH， |
| E | 38.3 | 1.35 | 13.9 | 1.46 | 2.99 | α-FeOOH，NiFe 2O 4 |
| F | 52.1 | 1.15 | 5.5 | 0.89 | 3.01 | α-FeOOH，NiFe 2O 4 |
[table 2]
| Classification | Catalyzer limonite symbol | Median size after the pulverizing (μ m) | Specific surface area (m after the pulverizing 2/g) | Coal transformation efficiency (quality %) | Dissolve in the yield (quality %) of the composition of hexane |
| Embodiment 1 | A | 0.8 | 40.4 | 95.3 | 46.8 |
| Embodiment 2 | B | 0.8 | 44.5 | 95.6 | 51.7 |
| Embodiment 3 | C | 0.9 | 58.1 | 95.1 | 49.2 |
| Comparative example 1 | D | 0.8 | 64.1 | 92.3 | 34.8 |
| E | 0.7 | 51.7 | 93.4 | 42.8 | |
| F | 0.8 | 48.1 | 93.8 | 41.9 |
[table 3]
| Classification | Catalyzer limonite symbol | S/Fe (atomic ratio) | Coal transformation efficiency (quality %) | Liquefaction oil transformation efficiency (quality %) | Gaseous constituent yield (quality %) |
| Embodiment 4 | B | 2.0 | 99.4 | 49.7 | 17.5 |
| Embodiment 5 | B | 0.5 | 94.6 | 31.6 | 22.9 |
Compare with existing method of liquefying coal, increased the oil content yield according to relevant its catalytic activity height of coal liquefaction method of the present invention. For this reason, become possibility so that reach high oil content yield with a small amount of catalyst addition. Accordingly, say coal liquefaction favourable from economic angle.
Claims (5)
1. method of liquefying coal, this method is to comprise iron ore below the median size 10 μ m of use mechanical disintegration in coal liquefaction solvent as catalyzer, and under solvent and catalyzer and sulphur and/or sulfide existence, coal is carried out the method for liquefying coal of the hydrogenation operation of hydrogenation, it is characterized in that, as the iron ore that uses as above-mentioned catalyzer is iron level: more than the 40 quality %, nickel content: 0.2～2.5 quality %, aluminium hydroxide content: 6～20 quality %, chromium content: the limonite that 1.4 quality % are following, wherein, iron in the described limonite is to contain as the iron cpd that contains alpha-feooh, the amount of described sulphur and/or sulfide is with wherein the sulfur content and the atomic ratio of the iron amount in the described limonite, and promptly the S/Fe atomic ratio measuring is 1.0～5.0.
2. by the described method of liquefying coal of claim 1, wherein, described iron cpd is the iron cpd of oxygen-free iron.
3. by claim 1 or 2 described method of liquefying coal, wherein, the nickel in the described limonite is as containing NiFe
2O
4Nickel compound contain.
4. by the described method of liquefying coal of claim 1, wherein, the nickel in the described limonite is as NiFe
2O
4Contain.
5. by the described method of liquefying coal of claim 1, wherein, use the solid Sulfur as described sulphur.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34866999A JP2001164263A (en) | 1999-12-08 | 1999-12-08 | Method for liquefying coal |
| JP348669/1999 | 1999-12-08 |
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| Publication Number | Publication Date |
|---|---|
| CN1298920A CN1298920A (en) | 2001-06-13 |
| CN1145685C true CN1145685C (en) | 2004-04-14 |
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ID=18398567
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001352377A Expired - Lifetime CN1145685C (en) | 1999-12-08 | 2000-12-08 | Process for coal liquefaction |
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|---|---|
| JP (1) | JP2001164263A (en) |
| CN (1) | CN1145685C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104607192A (en) * | 2015-01-23 | 2015-05-13 | 上海大学 | Coal electrolysis hydro-liquefaction catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457261C (en) * | 2005-04-27 | 2009-02-04 | 中国石油化工股份有限公司 | Iron-based coal liquefied catalyst and production thereof |
| JP5193432B2 (en) * | 2006-04-26 | 2013-05-08 | 国立大学法人九州工業大学 | Method for producing string-like carbon and method for using the same |
| CN100448945C (en) * | 2006-09-14 | 2009-01-07 | 严绥 | Dry coal direct hydrocracking oil-preparing reactor and cracking oil-preparing process |
| CN100441663C (en) * | 2006-12-01 | 2008-12-10 | 王守峰 | Fluidization hydrogenation liquefaction method for coal |
| CN101280207B (en) * | 2007-04-04 | 2011-04-20 | 中国石油化工股份有限公司 | Method for direct liquefaction and comprehensive utilization of ravens |
| CN101429440B (en) * | 2007-07-25 | 2012-05-30 | 汉能科技有限公司 | Method for direct liquefaction of coal |
| CN102233279B (en) * | 2010-04-23 | 2013-04-17 | 金军 | Direct coal hydrogenation liquefaction catalyst and direct coal hydrogenation liquefaction method |
| CN103949255B (en) * | 2014-04-15 | 2016-08-17 | 福建三聚福大化肥催化剂国家工程研究中心有限公司 | A kind of residual oil hydrocatalyst and its preparation method and application |
| CN106732606B (en) * | 2016-12-27 | 2019-10-15 | 陕西师范大学 | A kind of kerosene co grinding method ferrum-based catalyst |
-
1999
- 1999-12-08 JP JP34866999A patent/JP2001164263A/en active Pending
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104607192A (en) * | 2015-01-23 | 2015-05-13 | 上海大学 | Coal electrolysis hydro-liquefaction catalyst and preparation method thereof |
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