CN1014418B - Method of liquefying coal - Google Patents
Method of liquefying coalInfo
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- CN1014418B CN1014418B CN 85107623 CN85107623A CN1014418B CN 1014418 B CN1014418 B CN 1014418B CN 85107623 CN85107623 CN 85107623 CN 85107623 A CN85107623 A CN 85107623A CN 1014418 B CN1014418 B CN 1014418B
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Abstract
When lower grade iron ore is used as a coal liquefaction catalyst, in order to increase the catalytic activity of the lower grade iron ore, the lower grade iron ore is processed by the following one or at least two kinds of processing, such as reduction processing, heat processing or water processing for a long period or soak processing in water, and thus, substances harmful to the catalyst is removed before the iron ore is used as the catalyst. When high grade iron ore is used, the iron ore is reduced by carbon monoxide and then can be used as the catalyst.
Description
The present invention relates at high temperature, high pressure and under the catalytic condition of catalyst for coal liquefaction, is the method that hydrogenolytic cleavage makes gelatin liquefaction by hydrogenization.Therefore, coal will be placed in the special-purpose solvent that liquefies and carry out hydrogenation.
Method of liquefying coal comprises the direct liquefaction method.In this method, under high temperature and high pressure, feed hydrogen, so that carry out hydrogenolytic cleavage.Adopt this method, the consumption of hydrogen is very big, and the condition of hydrogenation is also very harsh.In order to improve reaction conditions, to use various catalyzer usually, for example, the oxide compound of cobalt, molybdenum, tungsten, tin, iron and lead etc. or halogenide, from above-mentioned catalyzer, select a kind of use, make above-mentioned reaction to carry out.But, do not have in the above-mentioned catalyzer a kind ofly can satisfy desired service performance fully, as the liquefying activity height, cost is low and a large amount of supply with etc.
For example, in traditional hydrogen-carbon method, be that 100 parts coal calculates with weight, in the boiling water reaction tower, add weight and be 10 parts ball shape Co-Mo catalyzer, make coal slurry pass through this tower, so that coal and hydrogen are at the about 450 ℃ of hydrogen pressure 150～220kg/cm also of temperature
2Condition under react.But because this catalyzer costs an arm and a leg, therefore the cost of this method also is very high.
Using iron ore is well-known method as the ferric iron catalyzer, because iron ore price is cheap, and has the advantage that can supply with in a large number.Yet, do not talk above-mentioned advantage for the time being, if above-mentioned iron ore uses as catalyzer without just handling, so, its liquefying activity is very low.For this reason, add sulphur or its compound as promotor, so that improve liquefying activity.Regrettably when a large amount of use sulphur or its compound, their can be present in the liquefaction oil with tangible content, thereby have reduced the quality of liquefaction oil.
The object of the present invention is to provide the method for the very high liquefaction coal of a kind of transformation efficiency.This method has improved the activity of the liquefaction coal of the catalyzer of being made up of iron ore, therefore compare with the traditional method of using iron ore, liquefaction reaction can carry out under lower temperature and lower pressure, and need not use promotor, only needs a spot of catalyzer.
In order to reach above-mentioned purpose of the present invention, iron ore of low ore grade will be through Overheating Treatment, reduction reaction and for a long time washing or in water, soak, and treatment process can be wherein a kind of, treatment process while and usefulness that also can be two or more be so that improve activity of such catalysts.Iron ore of low ore grade through handling like this can use as catalyzer.(also can be used as catalyzer with carbon monoxide reductive high grade iron ore.）
The method according to this invention, low-grade or high grade iron ore is just using as catalyzer after treatment.Therefore, can improve the catalytic activity of iron ore like this, thereby liquidation of coal reaction can be carried out under lower temperature and less pressure condition, and transformation efficiency is higher than traditional method.In addition, owing to do not need to use a large amount of promotor, so the quality of product can not reduce yet.
Accompanying drawing 1 shows Fe
2O
3By the changes in weight after the CO reduction.
The iron ore of low ore grade catalyst has improved activity. The composition of employed best iron ore of low ore grade is in the inventive method: the nickel of 0.3～3wt%, the iron of 10～50wt% and the chromium of 0.5～10wt%, and Al2O
3/SiO
2Ratio be 3 or less than 3, specific area is 50～100m2/ g. Red bauxite is exactly a kind of in this iron ore of low ore grade. Use has iron ore of low ore grade the reasons are as follows as catalyst of above-mentioned rerum natura: as catalyst, iron, nickel and chromium all have the effect that can provide for the hydrogenation of aromatic compound active. When the nickel content in the iron ore increased, the content of iron will certainly reduce. When nickel content was 0.5～3wt%, iron content was 50～10wt%. The test of carrying out according to the present invention, nickel content can provide active for hydrogenation significantly at the iron ore of above-mentioned content range. As for the content of chromium, when it is lower than 0.5wt%, just can not obtain above-mentioned effect. Equally, when chromium content surpasses 10wt%, can not obtain very good effect. But, when chromium content is in above-mentioned scope, just can obtain fabulous effect. Therefore, the content of iron, nickel, chromium is preferably in the above-mentioned scope in the iron ore.
Al
2O
3And SiO2Has the acidic catalyst activity. But, work as Al2O
3/SiO
2Ratio surpass at 3 o'clock, catalytic activity will reduce. In addition, with alumina (Al2O
3) changing into the compound of metallic spinel structure, its activity equally also can reduce. Therefore, Al2O
3/SiO
2Ratio preferably equals 3 or less than 3.
Improve the catalytic activity of iron ore from the physics aspect, specific area is an important factor. When the specific area of iron ore less than 50m2During/g, just can not obtain desirable activity. But the test of carrying out according to the present invention is when specific area surpasses 100m2During/g, can weaken catalytic activity equally. Therefore, specific area should be preferably in 50～100m2In/g the scope.
Yet, as mentioned above, if iron ore of low ore grade is unprocessed, just as catalyzer, its liquefying activity is not high so.This is because contain the deleterious material of catalyzer in this iron ore, for example alkaline metal salt or alkaline-earth metal salt.For example, in the lateritic ore, MgO, CaO, Na
2O, K
2Each content such as O is 3～10wt%, and the moisture absorption easily.
According to the present invention, in order to improve catalytic activity, iron ore of low ore grade will be through the treatment process of following one or more and usefulness:
(1) long-time water cleans or soaks in water, and dry immediately.
This processing can be removed objectionable impurities contained in the iron ore, resembles water-soluble alkali metal salts class or alkaline-earth metal salt etc., and has improved the catalytic activity of this iron ore.
Table 1-1 has shown that a method that washes with water removes the example of contained alkaline metal salt in the iron ore.
This processing is also in order to improving the specific surface area of iron ore, thereby improved the catalytic activity of iron ore.For example, after the water flushing, the specific surface area of iron ore is by original 64.0m
2/ g is increased to about 77m
2/ g.
Till this processing preferably proceeds to the pH value of soaking back solution in iron ore water flushing or in water and is 7.This is because the pH value of solution is 7 to show that alkaline metal salt and alkaline-earth metal salt have fully been disposed.After handling like this, must be with the iron ore drying.
(2) reduction reaction
Using carbon monoxide or hydrogen iron ore of low ore grade to be reduced in the process of handling, ferric oxide is reduced, and specific surface area improved, thereby has increased the catalytic activity of iron ore.Optimum treatmenting temperature is 200～500 ℃, and the treatment time should be above 120 minutes.Above-mentioned processing can be carried out in gas or solvent.
(3) thermal treatment
During thermal treatment,, answer bubbling air, so that increase specific surface area and improve the catalytic activity (best Heating temperature is 200～500 ℃) of iron ore in the iron ore of low ore grade heating.
Shown measured value as following table 1-2 through the specific surface area of thermal treatment and undressed iron ore of low ore grade sample.
Above-mentioned processing be with a kind of method carry out separately or two or more method simultaneously and with carrying out, preferred plan is as follows:
(1) reduction (carrying out separately)
(2) thermal treatment (carrying out separately)
(3) washing for a long time or immersion in water, dry and reduction immediately
(4) washing for a long time or in water, soak dry and thermal treatment immediately
(5) washing for a long time or immersion and dry immediately in water
(6) washing or immersion in water for a long time, drying, thermal treatment, reduction then
(7) washing for a long time or immersion in water, dry, reduction, thermal treatment then
After all objectionable impuritiess in the catalyst for coal liquefaction are removed and/or after its specific surface area increase, this catalyzer just can be used to make coal to produce hydrogenization.For the catalytic effect that obtains to stipulate, be that 100 parts coal calculates with weight, can add weight and be 1～10 part iron ore of low ore grade.The add-on of iron ore is lower than the add-on of iron ore of low ore grade in the traditional method.In traditional method, as the iron ore of low ore grade of catalyzer without any processing.In the present invention, removed objectionable impurities and specific surface area gets the iron ore of low ore grade that has increased even only use, the hydrogenation of coal reaction also can be carried out by very high transformation efficiency.Yet, in order further to improve transformation efficiency, can from the mixture of sulphur, sulfide or sulphur, select a kind of promotor, its addition is that 100 parts of coals are counted 0.1～10 part with weight.
Coal and catalyzer and solvent are in the same place.What made in the type of employed solvent and quantity and the traditional coal liquefaction method here is the same.For example, be that 100 parts coal calculates with weight, optimal addn is 100～200 parts a creosote.
Under high temperature and high pressure, hydrogen is added in the said mixture, so that make coal hydrogenation and become liquid.The temperature and pressure of hydrogenation is all low than hydrogenation temperature and pressure in the traditional coal liquefaction method that uses iron ore.For example, in traditional method, hydrogenation is to carry out under 450 ℃ temperature, and initial hydrogen pressure is 250Kg/cm
2, and in the method for the invention, hydrogenation is 100Kg/cm at 400 ℃ temperature, initial hydrogen pressure
2Just can carry out down.
Employed in the method for the invention high grade iron ore is best iron ore, its iron-holder be 50～70%(by weight).Al in this iron ore
2O
3/ SiO
2Ratio is 0.1～2.0, and specific surface area is 1～30m
2/ g.Resembling limonite or rhombohedral iron ore this is that the iron ore of main ingredient is exactly the example of high grade iron ore with the ferric oxide.This is because as catalyzer, the component of this iron provides active can for the hydrogenation of aromatics, so the very high iron ore of this iron-holder is very desirable as catalyzer.Work as Al
2O
3/ SiO
2When ratio is very big, this iron ore will show as the acidic catalyst activity.But, as Al
2O
3/ SiO
2Ratio is excessive, and this catalytic activity will reduce, and alumina (Al
2O
3) will change into a kind of compound of metallic spinel structure.For this reason, Al
2O
3/ SiO
2Ratio should be preferably in the above-mentioned scope.
From the activity of physics aspect raising as the iron ore of catalyzer, specific surface area is an important factor.When specific surface area departed from the scope of defined, the liquidation of coal activity will reduce.Like this, specific surface area is preferably in the above-mentioned scope.
According to the present invention, the high grade iron ore directly is not used for doing catalyzer, and only could use after with the carbon monoxide reduction.Handle by reduction, iron oxide reduction becomes FeO or metallic iron.
Fig. 1 shows FeO
3The changes in weight of sample when being reduced by carbon monoxide.The FeO or the metallic iron that generate can be from Fe
2O
3Estimate in the minimizing of the weight of sample.The weight of this sample reduced before this, increased (when reducing under 450 ℃ or 500 ℃ of conditions, this point is fairly obvious) then again, and this is because the carbon laydown that reduction is generated in handling causes at sample surfaces.
Now the present invention is described with the method for illustrative example.Below described in each example iron ore type and use before treatment process as shown in table 2.
Table 2
The washing or
The thermal treatment reduction in water of iron ore type is handled and is added sulphur
Soak
Example 1 iron ore of low ore grade O X O (CO) O
Example 2 iron ore of low ore grade O X O (CO) X
Example 3 iron ore of low ore grade X X O (CO) O
Example 4 iron ore of low ore grade O O O (CO) O
Example 5 iron ore of low ore grade O O O (CO) X
Example 6 iron ore of low ore grade X O X O
Example 7 iron ore of low ore grade X O X X
Example 8 iron ore of low ore grade O X O (H
2) O
Example 9 iron ore of low ore grade O X O (H
2) X
Example 10 iron ore of low ore grade X X O (H
2) O
Example 11 iron ore of low ore grade O X X O
Example 12 iron ore of low ore grade O X X X
Comparative example 1 iron ore of low ore grade X X X O
Example 13 high grade iron ore X X O (CO) O
Example 14 high grade iron ore X X O (CO) X
Example 15 high grade iron ore X X O (CO) O
Comparative example 2 high grade iron ore X X X O
O: treated
X: undressed
Example 1
The granularity of employed coal is 60 orders (250 μ m or thinner) in this example, and its characteristic provides in as following table 3.The iron ore of low ore grade catalyzer is by iron ore of low ore grade was soaked in distilled water 100 hours, then water flushing, drying under reduced pressure, and down feed the carbon monoxide gas streams at 350 ℃ and reduce and be prepared from, the composition and the specific surface area of this iron ore are listed in table 4.The coal dust of 50 grams, the sulphur of the iron ore of low ore grade of 1.5 grams and 0.3 gram mixes, and this mixture is put into 1 liter shake still.Allow the mixture be 100Kg/cm at initial hydrogen pressure
2G, temperature is reaction 30 minutes under 400 ℃ the condition, will carry out extraction test and gasometry to the component content of prepared product then.As shown in table 3, test-results shows that with reaction conversion ratio after tetrahydrofuran (THF) (THF) extracting be 91.8%.Here said transformation efficiency is meant the ratio (for example, oil, asphaltene, pre-asphaltene) of gas and the total content of THF soluble material in hydrogenated products (dried alkali, ashless alkali).Hereinafter employed transformation efficiency is same as above.
Table 3(Drumhellar)
The total industrial analytical element analysis of water
Content (%) is (d.a.f%) (d.b%)
Ash VM FC C H S H Odiff
13.4 9.7 46.8 43.5 74.1 4.9 0.4 1.7 18.9
D.b: dried alkali
D.a.f: ashless dried alkali
Ash: ash
VM: volatizable material
FC: fixed carbon
21
Table 4
| Type | Form (wt%) | Al 2O 3/SiO 2 | Specific surface area (m 2/g) | ||||||
| T oFe | SiO 2 | Al 2O 2 | MgO | CaO | Na 2O K 2O | Ni | |||
| Toronto Palawan | 42.0 | 10.5 | 9.6 | 3.4 | 0.04 | 0.12 | 0.8 | 0.92 | 64 |
Table 5
Type hydrogenated products (wt%) transformation efficiency
Gas THF soluble substance (%)
Toronto 8.2 83.6 8.2 91.8
Example 2
This example uses coal and the low-grade iron ore catalyzer identical with example 1 to make gelatin liquefaction, and except not adding sulphur, other operational conditions are identical with example 1.Measured result is as shown in table 6.
Table 6
Type hydrogenated products (wt%) transformation efficiency
Gas THF soluble substance residue (%)
Toronto
Palawan 8.4 75.4 14.2 85.8
Example 3
The granularity of employed coal is 60 orders or thinner in this example, and its characteristic is as shown in table 3.The iron ore of low ore grade catalyzer is by iron ore being ground to form 200 orders or thinner powder (74 μ m or littler) is prepared from, and it is formed and specific surface area provides in table 4.This catalyzer is by reduce two hours (pressure: 30Kg/cm with carbon monoxide gas
2G; Temperature: 400 ℃), then use the argon replaces entrap bubble, cooling is prepared from then.With 50 gram coals, the sulphur of the treated iron ore of 1.5 grams and 0.3 gram mixes with the wooden pomegranate oil of 75 grams, then the mixture that obtains is put into 1 liter and shakes still.Allow this mixture be 100Kg/cm at initial hydrogen pressure
2G and temperature are reaction 30 minutes under 400 ℃ the condition, also will carry out the extraction test and the gasometry of product content.It is as shown in table 7 to record the result.
Table 7
Type hydrogenated products (wt%) transformation efficiency
Gas THF soluble substance residue (%)
Toronto
Palawan 8.2 82.6 9.2 90.8
Example 4
The granularity of employed coal is 60 orders or thinner in this example, and its characteristic is as shown in table 3.The iron ore of low ore grade catalyzer is prepared from by iron ore of low ore grade, and the composition and the specific surface area of iron ore of low ore grade are listed in table 4.This Preparation of catalysts process is to soak in distilled water 100 hours, under the situation of 500 ℃ of bubbling airs, heat-treated 2 hours, at 350 ℃ down with carbon monoxide gas reductase 12s hour.With the coal of 50 grams, the sulphur of the iron ore of low ore grade catalyzer of 1.5 grams and 0.3 gram mixes with the creosote of 75 grams, then the mixture of making is put into 1 liter and shakes still.Allow this mixture be 100Kg/cm at initial hydrogen pressure
2G, temperature is reaction 30 minutes under 400 ℃ the condition, also will carry out product composition extraction test and gasometry.According to the result that records who lists in the table 8, the transformation efficiency after tetrahydrofuran (THF) (THF) extracting is 92%.
Table 8
Type hydrogenated products (wt%) transformation efficiency
Gas THF soluble substance residue (%)
Toronto
Palawan 8.2 83.8 8.0 92.0
Example 5
This example use with example 4 in identical coal and iron ore of low ore grade catalyzer carry out liquidation of coal, all the other operational conditions are all identical with example 4 except not adding sulphur.Record the result as shown in the following Table 9.
Table 9
Type hydrogenated products (wt%) transformation efficiency
Gas THF soluble substance residue (%)
Toronto
Palawan 8.0 77.0 13.0 85.0
Example 6
The granularity of employed coal is 60 orders or thinner in this example, and its characteristic is as shown in table 3.Iron ore of low ore grade Preparation of catalysts process is to soak iron ore 100 hours in distilled water (its form and specific surface area as shown in table 4), is 500 ℃ in temperature then and also heat-treats 2 hours under the condition of bubbling air.The coal of 50 grams, the iron ore of low ore grade catalyzer of 1.5 grams and 0.3 gram sulphur and 75 restrain the creosote thorough mixing, and the mixture of making is put into 1 liter the still that shakes.Then, allow this mixture be 100Kg/cm at initial hydrogen pressure
2G and temperature are reaction 30 minutes under 400 ℃ the condition.Also to carry out the extraction test and the gasometry of product composition at last.As shown in table 10, after tetrahydrofuran (THF) (THF) extracting, transformation efficiency is 83.7%.
Table 10
Type hydrogenated products (wt%) transformation efficiency
Gas THF soluble substance residue (%)
Toronto
Palawan 9.7 74.0 16.3 83.7
Example 7
This example use with table 6 in identical coal and iron ore of low ore grade catalyzer carry out liquidation of coal.Except not adding sulphur, other operational condition is all identical with example 6.It is as shown in table 11 to record test-results.
Table 11
Type hydrogenated products (wt%) transformation efficiency
Gas THF soluble substance residue (%)
Toronto
Palawan 8.2 59.4 32.4 67.6
Example 8
The granularity of employed coal is 60 orders or thinner in this example, and its characteristic is as shown in table 3.Iron ore of low ore grade Preparation of catalysts process is: soaked iron ore of low ore grade 100 hours in distilled water (its composition and specific surface area are as shown in table 4), then water washes, then drying under reduced pressure.After above-mentioned processing, this iron ore fed hydrogen reducing 2 hours down at 350 ℃.The coals of 50 grams, the creosote thorough mixing that the sulphur and 75 of the iron ore of low ore grade catalyzer of 1.5 grams and 0.3 gram restrains are put into the mixture of making 1 liter the still that shakes.Then, allow this mixture be 100Kg/cm at initial hydrogen pressure
2G and temperature are reaction 30 minutes under 400 ℃ the condition.Then, also to carry out the extraction test and the gasometry of product.Just as shown in Table 12, transformation efficiency is 92.3% after tetrahydrofuran (THF) (THF) extracting.
Table 12
Type hydrogenated products (wt%) transformation efficiency
Gas THF soluble substance residue (%)
Toronto
Palawan 8.6 83.7 7.7 92.3
Example 9
This example use with example 8 in identical coal and iron ore of low ore grade catalyzer, except not adding sulphur, with example 8 identical operations conditions under carry out liquidation of coal.The test-results that records is as shown in table 13.
Table 13
Type hydrogenated products (wt%) transformation efficiency
Gas THF soluble substance residue (%)
Toronto
Palawan 8.2 79.4 12.4 87.6
Example 10
The granularity of employed coal is 60 orders or thinner in this example, and its characteristic is as shown in table 3.Iron ore of low ore grade Preparation of catalysts process is: (its granularity is 200 orders or thinner to feed hydrogen stream reduction of low grade iron ore down at 350 ℃, its component and specific surface area are as shown in table 4) 2 hours, then use the argon replaces entrap bubble, reduce temperature then.With the coal of 50 grams, the creosote thorough mixing of the iron ore of 1.5 grams and 0.3 gram sulphur and 75 grams is put into the mixture of making 1 liter the still that shakes then.Allow this mixture be 100Kg/cm at initial hydrogen pressure
2G and temperature are reaction 30 minutes under 400 ℃ the condition, also will carry out the extraction test and the gasometry of product composition.The result who records is as shown in table 14.
Table 14
Type hydrogenated products (wt%) transformation efficiency
Gas THF soluble substance residue (%)
Toronto
Palawan 8.6 82.7 8.7 91.3
Example 11
The granularity of this routine employed coal is 60 orders or thinner, and its characteristic is as shown in table 3.Iron ore of low ore grade Preparation of catalysts process is: soaked low-grade iron ore (its granularity is 200 orders or thinner, and its component and specific surface area are as shown in table 4) 100 hours in distilled water, then water flushing, drying under reduced pressure then.
The coals of 50 grams, 1.5 gram iron ore of low ore grade catalyzer and 0.3 gram sulphur and the 75 creosote thorough mixing that restrain will be made mixture then and put into 1 liter and shake still.This mixture is 100Kg/cm at initial hydrogen pressure
2G and temperature are under 400 ℃ the condition after the reaction 30 minutes, also will carry out the extraction test and the gasometry of product component.
As shown in Table 15, the transformation efficiency after tetrahydrofuran (THF) (THF) extracting is 79.7%.
Table 15
Type hydrogenated products (wt%) transformation efficiency
Gas THF soluble substance residue (%)
Toronto
Palawan 9.7 70.0 20.3 79.7
Example 12
Carry out in this example in the employed coal of gelatin liquefaction and iron ore of low ore grade catalyzer and the example 11 identical, except not adding the sulphur, liquefaction condition also with example 11 in identical.The result who records is shown in table 16.
Table 16
Type hydrogenation reaction product (wt%) transformation efficiency
Gas THF soluble substance residue (%)
Toronto
Palawan 8.5 65.9 25.6 74.4
Comparative example 1
Employed coal is as shown in table 3 in this example.Employed iron ore of low ore grade catalyzer has component listed in the table 4 and character, and unprocessed before using.Liquidation of coal be with example 1 in carry out under the identical condition.What record the results are shown in the table 17.
Table 17
Type hydrogenation reaction product (wt%) transformation efficiency
Gas THF soluble substance residue (%)
Toronto
Palawan 8.2 67.4 24.4 75.6
Example 13
The granularity of employed coal is 60 orders or thinner in this example, and its characteristic is as shown in table 13.High grade iron ore Preparation of catalysts method is: with carbon monoxide (pressure: 30Kg/cm
2G; Temperature: 350 ℃) reducing iron ore 2 hours (component and the specific surface area of this iron ore are shown in table 18) is used the argon replaces residual gas, reduces temperature then.With 50 gram coals, 5 gram iron ores and 1 gram sulphur and 75 gram creosote uniform mixing, then this mixture is joined 1 liter shaking in the still.Can make this mixture at 100Kg/cm
2Reaction is 30 minutes under the initial hydrogen pressure of G and 400 ℃ the temperature.The composition of Huo Deing will pass through extraction test and gasometry like this.Shown in table 19, after tetrahydrofuran (THF) (THF) extracting, the transformation efficiency of iron ore A and iron ore B is respectively 93.4% and 99.6%.
Table 18
Iron ore main component (wt%) Al
2O
3Specific surface area
T.Fe SiO
2Al
2O
3CaO /SiO
2（m
2/g）
A 59.2 4.38 2.60 2.60 0.59 10
（Hamersley）
B
（Timblo Goa） 60.0 0.56 3.01 3.01 1.18 13
Table 19
Iron ore hydrogenation reaction product (wt%) transformation efficiency
Gas THF soluble substance residue (%)
A 8.4 85.0 6.6 93.4
（Hamersley）
B 8.8 90.9 0.3 99.6
（Timble Goa）
Example 14
With so that identical in the coal of gelatin liquefaction and high grade iron ore and the example 13, except not adding the sulphur, liquefaction condition is also identical with example 13 in this example.The result who records is shown in table 20.
Table 20
Iron ore hydrogenation reaction product (wt%) transformation efficiency
Gas THF soluble substance residue (%)
A 8.8 76.5 14.7 85.3
（Hamersley）
B 8.1 85.9 9.6 90.4
（Timblo Goa）
Example 15
The granularity of employed coal is 60 orders or thinner in this example, and its characteristic is as shown in table 3.High grade iron ore Preparation of catalysts method is: 5 gram iron ores (it has component and the specific surface area of listing in the table 18) are mixed with 75 gram creosotes, with carbon monoxide (pressure: 30Kg/cm
2G; 350 ℃ of temperature) make this mixture reductase 12 hour, use the argon replaces entrap bubble, reduce temperature then.When 50 gram coals, after 5 gram iron ores and 1 restrain sulphur and the reductive creosote mixes, this mixture is joined 1 liter shaking in the still.Can make this mixture at 100Kg/cm
2Reaction is 30 minutes under the initial hydrogen pressure of G and 400 ℃ the temperature, and the component of making is through extraction test and gasometry.The result who obtains thus is shown in table 21.
Table 21
Iron ore hydrogenation reaction product (wt%) transformation efficiency
Gas THF soluble substance residue (%)
A 8.4 84.0 7.6 92.4
（Hamersley）
B 8.8 88.2 3.0 97.0
（Timblo Goa）
Comparative example 2
Employed coal is identical with example 13 in this example.The iron ore of employed high grade iron ore component as shown in Table 18 and specific surface area, unprocessed before using.Make the condition of gelatin liquefaction the same with condition in the example 13.Measured result is as shown in Table 22.
Table 22
Iron ore hydrogenated products (wt%) transformation efficiency
Gas THF soluble substance residue (%)
A 9.2 62.4 28.4 71.6
（Hamersley）
B 8.8 70.3 20.9 79.1
（Timblo Goa）
Claims (14)
1, a kind of liquefaction coal is produced the method for hydrogenated products, wherein the total content of gas and THF soluble material is not less than 85.0 with the ratio of total hydrogenated products, this method is included in laterite ores and does under liquidation of coal catalyzer and the existence of no sulphur compound, the hydrogen of High Temperature High Pressure is added in the mixture of coal and solvent, described laterite ores contains 10-50% (weight) iron, has 50-1000m
2The specific surface area of/g and process are included in to flood for a long time or wash in the water is enough to dissolve catalyzer poison, drying, heating, then with the improvement processing of all steps of reducing gas reductive in interior catalytic activity.
2, method according to claim 1, the consumption that wherein is used to improve the laterite ores of catalytic activity is counted the 1-10 weight part with the coal of 100 weight parts.
3, method according to claim 2, wherein reducing gas is select from carbon monoxide and hydrogen at least a, and the reduction processing is carried out at 200 ℃-500 ℃.
4, method according to claim 1, wherein laterite ores is heated to 200 ℃-500 ℃.
5, a kind of liquefaction coal is produced the method for hydrogenated products, wherein the soluble material total content of gas and TGF is not less than 90.8 with the ratio of total hydrogenated products, this method is included in that laterite ores is made the liquidation of coal catalyzer and a kind of promotor that is selected from sulphur, sulphur compound and composition thereof exists down, High Temperature High Pressure hydrogen is added in the mixture of coal and solvent, described laterite ores contains 10-50%(weight) iron, have 50-100m
2The specific surface area of/g, and through being included in the water long-time dipping or washing to be enough to dissolve poisonous substance, handle in the improvement of interior catalytic activity with the Primordial Qi reduction then.
6, method according to claim 5, the consumption that wherein is used to improve the laterite ores of catalytic activity is counted the 1-10 weight part with the coal of 100 weight parts.
7, method according to claim 5, wherein reducing gas is select from carbon monoxide and hydrogen at least a, and the reduction processing is carried out at 200 ℃-500 ℃.
8, method according to claim 5, wherein laterite ores is heated to 200 ℃-500 ℃.
9, a kind of liquefaction coal is produced the method for hydrogenated products, wherein the soluble material total content of gas and THF is not less than 85.8 with the ratio of total hydrogenated products, this method is included in laterite ores and makes liquidation of coal catalyzer and no sulphur or sulphur compound existence down, High Temperature High Pressure hydrogen is added in the mixture of coal and solvent, described laterite ores contains 10-50%(weight) iron, have 50-100m
2The specific surface area of/g, and dissolve poisonous substance, drying, handle in the improvement of interior catalytic activity in interior step with all steps of reducing gas reductive then being enough to through being included in the water long-time dipping and washing.
10, method according to claim 9, the consumption that wherein is used to improve the laterite ores of catalytic activity is counted the 1-10 weight part with 100 weight part coals.
11, method according to claim 9, wherein reducing gas is select from carbon monoxide and hydrogen at least a, and the reduction processing is carried out at 200 ℃-500 ℃.
12, method according to claim 9 wherein in 100 weight part coals, adds a kind of promotor that is selected from sulphur, sulphur compound and composition thereof of 0.1-10 weight part.
13, a kind of method of liquefaction coal, this method is included in that laterite ores is made the liquidation of coal catalyzer and a kind of promotor that is selected from sulphur, sulphur compound and composition thereof exists down, High Temperature High Pressure hydrogen is added in the mixture of coal and solvent, described laterite ores contains 10-50%(weight) iron, have 50-100m
2The specific surface area of/g, and through being included in the water long-time dipping being enough to dissolve catalyzer poison, drying, improving in interior catalytic activity with all steps of carbon monoxide gas reductive and handle then, thus obtain being not less than 91.8 transformation efficiency.
14, method according to claim 13, wherein in 100 weight part coals, a kind of promotor that is selected from sulphur, sulphur compound and composition thereof of 0.1-10 weight part in addition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85107623 CN1014418B (en) | 1984-09-29 | 1985-09-27 | Method of liquefying coal |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20423184A JPS6183284A (en) | 1984-09-29 | 1984-09-29 | Liquefaction of coal |
| CN 85107623 CN1014418B (en) | 1984-09-29 | 1985-09-27 | Method of liquefying coal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85107623A CN85107623A (en) | 1987-04-08 |
| CN1014418B true CN1014418B (en) | 1991-10-23 |
Family
ID=25742114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85107623 Expired CN1014418B (en) | 1984-09-29 | 1985-09-27 | Method of liquefying coal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1014418B (en) |
Families Citing this family (1)
| 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 |
-
1985
- 1985-09-27 CN CN 85107623 patent/CN1014418B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN85107623A (en) | 1987-04-08 |
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