Liquefaction of resinous brown coal

The process according to the invention is carried out in such a way that the coal to be subjected to hydrogenation in the liquid state is partially deoxygenated and at the same time decerboxylated by heating from the simultaneous removal of carbon dioxide, water vapor and small amounts of carbon monoxide. and light hydrocarbons having from 1 to 4 carbon atoms.

The heating of the coal before the hydrogenation in the liquid state is carried out in such a way that at least 10% of the organically bound oxygen is removed, preferably 15 to 60 or even more% of the organically bound oxygen is removed. pressure not exceeding 1.07 MPa, usually at a pressure of 0.107 to 1.07 MPa · Heating is continued until the oxygen is removed to the desired degree, usually 0.05 to 2 hours ·

Obviously, although hydrogenation in the liquid state is usually carried out in known dense solvents, it is equally well possible to remove oxygen from pitch lignite and / or lignite in longer dense solvents that are different from those commonly used for other hydrogenation solvents. degree·

Pre-heating of lignite and / or lignite to remove oxygen minimizes the amount of hydrogen required in liquid phase hydrogenation · Lignite and / or lignite has been found to typically have an oxygen content of 15 to 30% compared to bituminous coal that usually has an oxygen content of 4 to 12% by weight ·

That is, if the pitch of the pitch and / or the lignite of oxygen is freed from the process according to the invention, the hydrogen consumption in the next hydrogenation stage, which is carried out in the liquid phase, decreases substantially.

In the process according to the invention, the hydrogenation of pitch and / or lignite in the liquid phase is carried out in a solvent derived from pitch and / or lignite, the solvent comprising at least 25% by weight of components having a boiling point above 425 ° C. preferably 35 to 70% by weight of the components having a boiling point above 425 ° C · 5% by volume of the solvent preferably distills at a temperature of at least 29 ° C, although the solvent may also contain lower boiling components · The composition according to claim 1, wherein the solvent may contain components with a boiling point lower than 290 ° C only if it contains at least 25% by weight of components with a boiling point higher than 425 ° C. It goes without saying that all temperatures are corrected to atmospheric pressure.

The process according to the invention is therefore based on the finding that by using a solvent which originates from the type of coal to be treated with a boiling point greater than 425 ° C of at least 25% by weight when hydrogenating pitch coal and / or lignite The dispersed state of the coal, whereas, if these properties of the solvent are not adhered to, the coal loses its ability to retain the dispersion, so that it accumulates in the reactor, causing a too high pressure drop.

Liquid phase hydrogenation of pitch lignite and / or lignite is usually carried out at temperatures of 315 to 480 ° C at a pressure of 20 to 50 psig. In the liquid state, a space velocity of the order of 0.3 to 4.0 hours is usually used

The liquid phase hydrogenation is usually carried out in the presence of a catalyst of this hydrogenation. The catalyst is typically a Group VIB and / or VIII metal oxide and / or sulfide on a suitable support, for example on alumina or a mixture of silica and alumina. Preferred catalysts are, for example, cobalt and molybdenum, nickel and molybdenum sulfides, or nickel and tungsten · The catalyst may be granulated in shape, in the form of tablets, spheres or randomly shaped particles of varying size in the range of 4 to 40 mesh ·

The catalyst is contacted with the hydrogenation mixture in a variety of ways, for example, the catalyst may be added as a powder, or a catalyst may be used in solid, fluidized bed, etc. A preferred embodiment is to use the catalyst so that liquefied coal passes . The liquid phase hydrogenation is carried out in one or more reactors, preferably two or three reactors in series.

BRIEF DESCRIPTION OF THE DRAWINGS The invention will now be described in more detail with reference to the accompanying drawings, in which a schematic diagram is shown according to which the method according to the invention can be carried out.

The milled, partially dried pitch lignite and / or lignite with a water content of 3 to 15% is fed via line 10 to chamber 11. in which the coal is suspended in a dense solvent which is fed via line 12. The solidified solvent is from above. of said type, i.e. it comprises at least 25% by weight of components having a boiling point greater than 425 ° C. The slurry is generally heated at a temperature of 65 to 230 ° C at a pressure of 0 to 0.343 M * to give a slurry containing 25 to 45% by weight of coal.

When a slurry is formed, a small amount of water can be released, which is usually discharged in the form of steam from the chamber 11.

The carbon slurry or dispersion in the dense solvent is removed from chamber 11 via line 13 to chamber 4, whereby the slurry can be heated as described above, thereby removing oxygen from the coal while releasing the released products from chamber 13. In this, at least 10%, preferably 15 to 60%, of the organically bound oxygen initially present in the clay is removed.

The partially deoxygenated paste is then fed from the chamber. . It is also possible to mix the hydrogen-containing gas and the above paste before feeding it into the chamber 16. This chamber contains a catalyst of the above type and the hydrogenation of the pitch brown uil and / or lignite in the liquid state. As already mentioned, the paste 16 passes through the chamber 16 from bottom to top, preferably several, preferably 2 to 3, reactors in succession instead of the chamber. Of course, reactors of a different type may also be used for this purpose.

The gaseous hydrogenation products are discharged via line 18, while the remainder of the hydrogenation is discharged via line 19 from chamber 16. 7 some of the product is returned to line 15 via line 21, but in most cases this is not required.

The product in line 22 is fed to the distillation zone 23 where the lighter components are controlled. In zone 23, these materials are usually de-distilled by removing the components flowing at 290-315 ° C. These components are discharged via line 24 and form part of the pure product of this hydrogenation.

The residual product is discharged from zone 23 via line 25 and optionally a portion of it is returned to chamber komory and / or chamber 14. The feed is fed via line 26 to chamber 11 at most 15% by weight of the total amount of this residual product.

The remaining product in line 27 is fed to the mixing zone 28 where it is mixed with the liquid fed through line 29 to remove the ash product.

Usually, the liquid disclosed in U.S. Patent No. 3,856,675 is used for this purpose. This patent was granted on December 24, 1974 and discloses a liquid having a factor K of at least 9.75, preferably at least 11.0. This liquid allows the insoluble portion of the residual product to be present and comprises 5% by weight of the components which de-distil at a temperature of at least 120 ° C and 95% by volume of the components which de-distil within the temperature range of 175 to 400 ° C. the liquid comprises at least 5% by volume of components with a distillation temperature of at least

155 ° C, in particular at least 205 ° C. Preferably, 95% of the components distil at a temperature of not more than 315 ° C. The most preferred type of this liquid comprises 5 volume% components with a distillation temperature of at least 220 ° C and 95 volume% components with a distillation temperature of at most 260 ° C. This liquid is usually supplied in such an amount that:. the ratio of this liquid to the product is 0.5 to 1.0 parts by weight.

A mixture of said product and said liquid is discharged from the mixing zone 28 via line 32 and fed to chamber 33. ^{in which} remove ash and from which the ash-free product is removed. At the same time, ash is removed in another direction. As noted in the aforementioned US patent, the chamber 33 typically contains 1 to several members to aid in the settling of solid particles, the settling of these particles usually being carried out at a temperature of 205 to 315 ° C.

An insoluble material-free product is discharged from the top 33 of the chamber 33 to an area 12 in which it separates from the liquid for ash separation. This liquid is then discharged from zone 35 through line 36 and mixed with the liquid supplied through line 37 and then re-fed in the required amount through line 29 to the mixing zone 28.

The remainder of the product discharged from the top of the chamber 33 is divided into two streams, one of which is passed through line 12 to the chamber 11 and the other, if necessary, into a chamber 14 in which the coal dispersion is preheated via line 38. is removed via line 39 as a pure hydrogenation product.

The ash is removed from the chamber 33. ' from its lower part via line 41 and is fed to a zone 42 in which it separates from the remainder of the liquid which served to separate the ash. This liquid is then passed through line 31 back to the mixing zone 28.

The remainder of the ash is passed through line 43 for further processing, for example for the production of coke and / or for processing into gaseous products.

It goes without saying that the process according to the invention can be carried out in a number of other embodiments without departing from it. In particular, it is possible to carry out another method of removing ash.

In another possible embodiment of the process of the invention, in some cases, liquefaction may be carried out without the use of a solvent that passes from the treated material, and the solvent for liquefaction of pitch lignite and / or lignite may not necessarily contain heavier components as described above.

The invention will be illustrated by the following examples.

Example 1

The coal suspension, consisting of 429 g of brown coal, the analysis of which is given in Table X, and 1000 g of tar derived from lignite and previously hydrogenated at 290 ° C, are stored at 95 ° C in a 2 liter vessel. The mixture was then placed in an electrically heated 2 liter bomb, prewashed with nitrogen gas and equipped with a back pressure regulator. The bomb is sealed and a pressure of 0.98 bar is set on the regulator, with 6 Nm ^ / 400 h of hydrogen being fed to the bomb.

The outlet gas is cooled and passed to a water-cooled trap. The non-condensable gas from the scrubber is fed into the rubber bag via a flow meter. The liquid product of the bomb was heated to 315 ° C for 15 minutes and held at that temperature for 20 minutes. At the end of this time, read the flowmeter and disconnect and close the rubber gas bag.

It then analyzes the gases contained in the bag. The total amount of carbon dioxide is calculated and the total molar amount of the non-condensable gas fed through the flowmeter to the rubber bag is also calculated. This showed that 26% of the organically bound oxygen in the coal was released in the form of carbon dioxide.

Example 2

Example 1 was repeated using a 2 liter bomb, the bomb content consisting of 0 g of brown coal and 1000 g of lignite tar pre-hydrogenated at 290 ° C as in Example 1. No carbon dioxide was detected in the off-gas.

Example 3

A dense dispersion of coal containing 30% by weight of brown coal, the analysis of which is given in Table I and 70% by weight of thick solvent I of Table II, was prepared at 90 ° C in a stirred tank heated by steam. The solvent is prepared from pre-hydrogenated brown coal tar so that it is related to the solvent prepared from the actual material to be hydrogenated.

Said paste is fed through a metering pump into a spiral-shaped heating zone and mixed under a pressure of 8 with hydrogen-rich gas. During mixing, the mixture of carbon dispersion and hydrogen-rich gas is heated to 290 ° C. the fat mixture is then fed continuously to a bottom-up hydrogenation reactor. The conditions under which the hydrogenation is carried out are given in Table III.

The product from the reactor is fed to a separator heated with hot water to separate the gaseous and liquid parts. The gaseous product is fed to other parts of the plant via a controlled valve. As soon as the liquid content of the separator reaches 75-80% of the free space, this product is transferred to another separator which is under hydrogen pressure to achieve the same conditions. The contents of the first separator are then transferred to the next vessel under atmospheric pressure. From this vessel it is then fed to a container in which the product is constantly stirred and heated with steam. The sequence of the steps is repeated continuously.

This continuous brown coal treatment process was stopped after 48 hours of operation. A sample of the liquid was taken from the storage tank and the total amount of product stored as well as the tank temperature were also determined. The following values ​​were then determined: ash content, quinoline-insoluble matter content and specific gravity, as well as several temperature determinations. From the above data and from the weight of the product obtained, it was found that approximately 83-1% of the starting product fed to the hydrogenation reactor was converted to a quinoline soluble form, which can be considered as a measure of the liquefaction achieved. Over the course of the process, a pressure drop of 0.128 to 0.156 MPa was observed in the reactor.

Example 4

The procedure of Example 3 was repeated except that a slightly lighter thick solvent (Solvent II) was used, the characteristic of which is shown in Table IV. This solvent was also prepared from pre-hydrogenated brown coal tar and was related to the solvent prepared directly from the product to be treated. All other conditions were essentially the same as in Example 3. Table III lists the hydrogenation conditions for Example 4.

15 minutes after the start of the procedure, a rapid pressure drop of 1.07 MPa occurred. At the same time, the feed of the starting product was interrupted and heavy creosote oil from the associated storage tank was added to the hydrogenation tank. This oil was prepared from pitch brown coal.

After some time, there was an increase in pressure in the hydrogenation reactor, so that the total pressure drop was again only 0.128 to 0.156 MPa. The creosote oil feed was then interrupted and the original starting product was fed back into the hydrogenation reactor. After 15 minutes, the pressure drop again more than 1.07 MPa. This pressure drop completely interrupted the process. After depressurization, cooling and nitrogen purge, the reactor was opened and the catalyst layer, which was clogged with brown coal particles, was examined in more detail. Obviously, these particles were not well dispersed in the solvent and settled at the bottom of the catalyst, thereby substantially reducing the permeability of the entire catalyst layer.

Table 1

Analysis of ground, dried brown coal

Orientation analysis

<td>water, scales. % volatile matter, weight. % ash, weight. % bound carbon, weight. %</td><td> 6,02 51,48 0,86 47,66</td>

<td>Elemental analysis</td><td></td>

<td>water, scales. %</td><td> 6,02'</td>

<td>ash, scales. %</td><td> 0,81</td>

<td>carbon, weights. %</td><td> 63,07</td>

<td>hydrogen, weight. %</td><td></td>

<td>(after separation of hydrogen in water)</td><td> 3&gt;96</td>

<td>nitrogen, weights. %</td><td> 0,51</td>

<td>sulfur, scales. %</td><td> 0,24</td>

<td>organic oxygen, scales. % (subtraction)</td><td> 25,3*9</td>

<td>Calorific value (23,268 J / kg)</td><td> 10 980</td>

<td>Table II</td><td></td>

<td colspan="3">Solvent I of Example 3</td>

<td>Specific gravity 138/15 ° C</td><td> 10</td><td> 269</td>

<td>Specific gravity 227/15 ° C</td><td> 10</td><td> 224</td>

<td>Ash, scales. %</td><td></td><td> 0.17</td>

<td>sulfur, scales. %</td><td></td><td> 0,44</td>

<td>carbon, weights. %</td><td></td><td> 85,86</td>

<td>Hydrogen, weights. %</td><td></td><td> 9,35</td>

<td>nitrogen, weights. %</td><td></td><td> 0,49</td>

<td>benzene insoluble matter, weight. %</td><td></td><td> 1,5</td>

Vacuum distillation analysis

<td>Deetilovaný</td><td>Distilled</td><td>Temperature after Repair</td>

<td>share, ob;]. %</td><td>subjects, scales. %</td><td>to 760 torr</td>

<td> 0,0</td><td> 0,0</td><td> 220</td>

<td> 1,0</td><td> -</td><td> 267</td>

<td> 3,6</td><td> 3,29</td><td> 287</td>

<td> 9,0</td><td> 8,22</td><td> 315</td>

<td> 11.3</td><td> 10,41</td><td> 326</td>

<td> 21,3</td><td> 20,07</td><td> 354</td>

<td> 28,3</td><td> 26,76</td><td> 371</td>

<td> 35,0</td><td> 34,47</td><td> 383'</td>

<td> 45,0</td><td> 44,05</td><td> 402</td>

<td> 55,0</td><td> 53,40</td><td> ' 419</td>

<td> 58,6</td><td> 56,65</td><td> 426</td>

Table III

Liquid phase hydrogenation parameters of Examples 3 and 4

Catalyst shape catalyst content of coal in the mixture, weight. % paste solvent reactor type hourly space velocity hr^-1 (O^bmixture pressure / hour) volume m / s) pressure MPa feed rate g moo / 4.5 l hydrogen content mol. % reactor inlet temperature ° C reactor outlet temperature, ° C fresh molybdate. cobalt on alumina up to 10 mesh balls

30.0 in Examples 3 and 4 with a bottom-up flow reactor _t

1,7

137,2

0,1

285 to 315

415 to 421

Table 4

The solvent of Example 4

<td>specific gravity 225/15 ° C specific gravity 120/15 ° C</td><td> 0,995. 1 1,007</td>

<td>poppl, scales. %</td><td> 0,01</td>

<td>sulfur, scales. %</td><td> 0,37</td>

<td>scales, scales. %</td><td> 86,24</td>

<td>hydrogen, weight. %</td><td> 9,65</td>

<td>nitrogen, weights. %</td><td> 0,48</td>

continuation of Table IV

<td>Deetilized subdl, vol ·%</td><td>Distilled distillate, weight ·%</td><td>Temperature after repair to 760 torr ° C</td>

<td> 0</td><td> 0</td><td> 234</td>

<td> 3,4</td><td> 2,80</td><td> 255</td>

<td> 9,3</td><td> 8,75</td><td> 287</td>

<td> 19,2</td><td> 18,11</td><td> 315</td>

<td> 31,4</td><td> 29,98</td><td> 354</td>

<td> 45,7</td><td> 44,12</td><td> 371</td>

<td> 56,4</td><td> 54,48</td><td> 404</td>

<td> 66,5</td><td> 64,15</td><td> 410</td>

<td> 76,4</td><td> 73,78</td><td> 419</td>

<td> 82,6</td><td> 79,38</td><td> 427</td>

The advantage of the invention lies in the fact that it is possible to carry out the liquefaction of pitch brown lime and / or lignite without the use of an increased amount of hydrogen due to the partial removal of oxygen in accordance with the invention. to use a solvent which is derived from the starting material while ensuring a perfect dispersion in the solvent.