FI78496C - FOERFARANDE FOER FRAMSTAELLNING AV EN KOLVAETEBLANDNING. - Google Patents

Description

78496

Method for preparing a hydrocarbon mixture

The invention relates to a process for the preparation of a hydrocarbon mixture having a Ramsbottom Carbon Test value (RCT) of 5% by weight and an initial boiling point of T1 ° C.

RCT is an important parameter in evaluating the suitability of heavy hydrocarbon mixtures as feedstock for catalytic conversion processes such as catalytic cracking in the presence or absence of hydrogen to produce light hydrocarbon distillates such as gasoline and kerosene. If the RCT value of the feed is high, the catalyst is rapidly deactivated in these methods.

Mixtures of hydrocarbon residues, such as those obtained by distilling crude mineral oil and asphalt-containing bitumen, separated by removing bitumen from solvents from said distillation residues, or residues obtained by distillation, are generally over-hydrated and hydrotreated without pretreatment for use as feeds to the aforementioned catalytic conversion processes.

Since the RCT value in residual hydrocarbon mixtures is mainly determined as a percentage of the bitumens in the mixtures, a reduction in the RCT value of these mixtures can be achieved by lowering the bitumen content. This can in principle be achieved in two ways. Some of the bitumens can be separated from the mixture by solvents or some of the bitumens can be converted by subjecting the mixture to a catalytic hydrotreating. In order to reduce the RCT value of the distillation residue, the latter method is preferred, firstly because it gives a heavy product with a low RCT value and secondly, because, unlike the first method, where asphalt bitumen is obtained as a by-product, valuable Cc + atmospheric distillate is obtained as a by-product. Given that the yields of the first 35 methods for asphalt bitumen are poor, only the latter method is suitable for the preparation of a heavy product with a low RCT value from mixtures of asphalt bitumens and distillation residues. However, the disadvantage of the latter process is the increase in the formation of the undesired C 1-4 fraction, which in addition has a considerable effect on the hydrogen consumption of the process.

It has been found that when lowering the RCT by catalytic hydrotreatment of heavy hydrocarbon mixtures, where the catalytic hydrotreating is performed under more severe conditions to achieve a greater reduction in RCT, the parameter "C4" production per percent decrease in RCT "(hereinafter referred to as" G ") initially remains substantially constant (Gc) and then grows relatively sharply. However, for the hydrogen consumption of the process 15, it is important to ensure that the reduction of the RCT value is not performed below a value corresponding to G = 2 x Gc. In practice, this means that there are several cases where it is disadvantageous, starting from a heavy hydrocarbon mixture, to use a non-catalytic hydrotreating to produce a product which, after removal of atmospheric distillate, can give a product with an initial boiling point of T value of a weight percent. In these cases, however, there is an interesting way to prepare an oil from a heavy hydrocarbon mixture having an initial boiling point and an RCT value of the above. For this purpose, the product obtained from the catalytic hydrotreating is separated by distillation into an atmospheric distillate and an atmosphere into a residue having an initial boiling point of T 1 ° C. The method can be continued in two ways. First, so much bitumen can be separated from the atmospheric residue by means of solvents to obtain an atmospheric residue purified from bitumen with an RCT value of the desired α% by weight. Second, the atmospheric residue can be divided by vacuum distillation and vacuum residue, and so much bitumen can be separated from the vacuum residue by solvents to obtain a bitumen-purified residue having an RCT value of 3 78496 such that mixing this bitumen-purified vacuum residue with a pre-separated whose RCT value is the desired a weight percent. The most interesting balance between the yields of the C ^ fraction, C5 + atmospheric distillate, 5 bitumen and oil with an initial boiling point of T ^ ° C and an RCT value of α% by weight is obtained when the catalytic hydrotreating is carried out under conditions where G is 1.5 x Gc - 2 .0 x Gc. If the catalytic hydrotreating is carried out under conditions where G <1.5 x Gc, a small formation of C4 is still obtained, but the yield of an oil with an initial boiling point of Ti ° C and an RCT value of a% by weight in the combined process is unsatisfactory. If the catalytic hydrotreating is carried out under conditions where G> 2.0 x Gc, the combination process still yields an oil with an initial boiling point of T ^ ° C and an RCT value of α% by weight, but this involves too much C ^ formation.

The Gc value and the conditions under which G reaches a value of 1.5 x Gc to 2.0 x Gc can be determined from a graph obtained from several catalytic hydrotreating experiments with bituminous hydrocarbon mixtures at different intensities and giving the G values is plotted as a function of the intensity levels used. With the exception of one parameter, i.e. the rate of fluid passing through the catalyst, which changes, is kept constant under the other conditions in the experiments and is chosen to be the same as that used in the practical application of the process.

The present invention is therefore directed to a process for preparing a hydrocarbon mixture having an RCT value of 30% by weight and an initial boiling point of T 1 ° C, subjecting the bituminous hydrocarbon mixture to a catalytic hydrotreating to reduce its RCT value, separating the product obtained by distillation to atmospheric distillate T 1 ° C, whereby either the atmospheric residue purified from bitumen with an RCT value of the desired α% by weight is obtained from said atmospheric residue by removing the bitumen by dissolving it or the atmospheric residue is first partitioned by vacuum distillation and vacuum residue from which the a vacuum-5 residue having an RCT value such that, when this latter bitumen-purified vacuum residue is mixed with said vacuum distillate, a mixture having the desired RCT value of a% by weight is obtained, the process being characterized in that the aytic hydrotreating is performed under conditions in which the C 1 yield per percent reduction in RCT value ("G") is 1.5 x Gc to 2.0 x Gc, where Gc is the substantially constant G value that G: has when the catalytic hydrotreating has been carried out under mild conditions.

Considering the way in which the RCT values 15 of hydrocarbon mixtures are determined, three cases can be distinguished.

(a) The viscosity of the test hydrocarbon mixture is so high that it is impossible to determine the RCT value according to ASTM method D 524. In this case, the CCT value (Conradson Carbon Test value) of the mixture is determined according to ASTM method D 189 20 and the RCT value is calculated from the CCT value by the formula: RCT = 0.649 x (CCT) 1'44.

(b) The viscosity of the hydrocarbon mixture to be tested is such that the RCT value can be determined according to ASTM method D 524, but this method gives an RCT value greater than 20.0% by weight. In this case, as in case a) above, the CCT value of the mixture is determined according to ASTM method D 189 and the RCT value is calculated from the CCT value using the formula shown in a).

(C) The viscosity of the test hydrocarbon mixture shall be such that the RCT value can be determined according to ASTM method D 524 and this method gives an RCT value not exceeding 20,0% by weight. In this case, the values thus obtained are considered to be the RCT value of the mixture in question.

5 78496 In practice, for the measurement of the RCT of mixtures of vacuum distillates, atmospheric residues, bituminous distillation residues and vacuum distillates and bituminous distillation residues, the direct method 5 in (c) is sufficient in several cases. The RCT values for vacuum residues are measured using both the direct method in (c) and the indirect method in (b). For the measurement of the RCT value of bitumen, the indirect method described in a) is usually the only possible one. The method according to the invention is a two-step method, in which the reduction of the RCT value is achieved by lowering the bitumen content. In the first step of the process, the bitumen content is reduced by changing some of the bitumens by catalytic hydroxy treatment. In the second step of the process, the bitumen content is reduced by removing some of the bitumens with the aid of solvents. Bitumens contained in hydrocarbons usually contain a significant percentage of metals, especially vanadium and nickel. If such mixtures are subjected to a catalytic hydrotreating, for example a catalytic hydrotreating to reduce the RCT, as in the process of the invention, these metals will precipitate on the catalyst used to reduce the RCT, thus shortening its service life. Thus, bituminous hydrocarbon mixtures with a vanadium and nickel content greater than 50 ppm (by weight) r should preferably be dehydrated before contacting the mixtures with the catalyst used to lower the RCT. This metal removal can be very conveniently carried out by contacting the mixture in the presence of hydrogen with a catalyst containing more than 80% by weight of silica. Both silica-only catalysts and catalysts containing one or more metals having a hydrogenating effect, in particular with nickel and vanadium, on a support consisting mainly of silicon dioxide are suitable for this purpose. Highly suitable demetallization catalysts 6 78496 are those which meet certain given requirements for their porosity and particle size and are disclosed in NL patent application 7309387. If the process according to the invention removes metals from hydrocarbon mixtures in the presence of hydrogen, this demetallization can be carried out in a separate reactor. Since the catalytic dewatering and the catalytic reduction of the RCT can be performed under the same conditions, both procedures can be carried out very suitably in the same reactor successively containing the layers of the dewatering catalyst and the catalyst used for the reduction of the RCT.

It should be noted that in catalytic metal removal, lowering the metal content is associated with a slight decrease in RCT. The same is true for the catalytic reduction of the RCT value 15, where the decrease in the RCT value is accompanied by a slight decrease in the metal content. In this patent, the reduction of the RCT value is to be considered as the total reduction of the RCT value in the catalytic hydrotreating (i.e., including the reduction of the RCT value that occurs in the possible catalytic deacidification treatment).

Suitable catalysts for performing catalytic RCT reduction include those containing at least one metal selected from the group consisting of nickel and cobalt and at least one metal selected from the group consisting of molybdenum and tungsten on a support containing more than 40% by weight of alumina. Highly suitable catalysts for lowering the RCT are those which form from nickel / molybdenum or cobalt / molybdenum metal combinations with supported alumina.

The catalytic reduction of the RCT value is preferably carried out at a temperature of 300-500 ° C, a pressure of 50-300 bar, a flow rate through the catalyst of 0.02-10 g.g * *, and a H2 / feed ratio of 100-5000 Nl / kg. Particularly preferably, the catalytic reduction of the RCT value is carried out at a temperature of 350-450 ° C, a pressure of 75-200 bar, a flow rate through the catalyst of 0.1-2 μg and a H 2 / feed ratio of 500-2000 Nl. / kg. The conditions used in the catalytic dewatering process in the presence of hydrogen, if performed if necessary, are the same as described above in connection with the reduction of the catalytic RCT value.

The desired reduction in RCT in the first step of the process of the invention can be obtained, for example, by using as the flow rate through the catalyst the rate corresponding to the reduction in RCT as read from the curve obtained from several catalytic hydrotreating experiments on bituminous hydrocarbon mixtures at different flow rates. through the catalyst and wherein the reduction in RCT achieved is shown as a function of the flow rates used through the catalyst. Apart from this flow rate, which varies, the other conditions in the experimental experiments are kept constant and are selected as those used in the application of the method according to the invention in practice.

The second step of the process according to the invention is the removal of bitumen by means of solvents applied to the residue obtained in the distillation of the hydrotreating product of the first step. The distillation residue to which the solvent removal step of the bitumen is subjected may be an atmospheric residue or a vacuum residue obtained from the hydrotreating product. Preferably, a vacuum residue obtained from the hydrotreated product is used for this purpose. Suitable solvents for solvent removal of bitumen include hydrocarbons having from 3 to 6 carbon atoms in their molecule, such as n-butane and mixtures thereof, such as mixtures of propane and n-butane, and mixtures of n-butane and n-pentane. A suitable solvent / oil weight ratio is between 7: 1-1: 1 and especially between 4: 1-2: 1. The removal of the bitumen by means of the solvent 35 is preferably carried out at a pressure of between 20 and 100 bar. If n-butane is used as the solvent, the removal of the bitumen is preferably carried out at a pressure of 35 to 45 bar and a temperature of 100 to 150 ° C.

If the reduction of the RCT value in the second step of the process according to the invention is carried out by removing the bitumen from the atmospheric residue with solvents, the desired RCT value of the bitumen-purified atmospheric residue can be obtained, for example, by using a temperature corresponding to the RCT value read from a curve carried out with the atmospheric residue at different temperatures, the RCT values of the obtained bitumen-purified atmospheric residues being shown with respect to the temperatures used. Apart from the variable temperature, the other conditions in the experimental experiments are kept constant and are selected in the same way as are used in the application of the method according to the invention in practice.

If the reduction of the RCT value of the second step of the process according to the invention is carried out by removing the bitumen from the vacuum residue and then mixing the bitumen-purified vacuum residue with the previously separated vacuum distillate, the RCT value and amount of bitumen-purified vacuum residue must be adjusted to match the vacuum distillate value and RCT as follows: If a given amount of vacuum distillate (VD) is available containing 25 parts by weight of a product having a given RCT ^ value, then to obtain a mixture having an RCT ^ value given by mixing the vacuum distillate with bitumen-purified vacuum residue (DVR) , B parts by weight of bituminous vacuum residue must be prepared, the RCTDVR value 30 of which is given by the equation: A x RCTvd + B x RCTDVR ^ ^ - m

A + B

35 or in other words: 9 78496 A (RCTm-RCTvd) = B (RCTdvr-RCTm)

In the above equation, the term on the left is known. In addition, the right-hand term RCTM is known.

5 Based on several research experiments on vacuum residues, for example at different temperatures, a graphical curve can be drawn in which the term B (RCTDVR-RCTM) is plotted as a function of the temperature used. In this case, the temperature used in the bitumen removal of the second stage of the method according to the invention can be determined from this curve and is the temperature at which the term A (RCTm-RCTvd) is given by the term B (RCTdvr-RCTm). With the exception of the variable temperature, other conditions in the bitumen removal test experiments are considered constant and are selected as those used in the application of the method of the invention.

In addition to the RCT value, the metal content is also an important parameter in studying the suitability of heavy hydrocarbon oils as feeds for catalytic conversion processes, with or without hydrogen, in the production of light carbon-20 hydrogen distillates such as gasoline and kerosene. If the metal content of the feed is relatively high, the catalyst is rapidly deactivated in these processes. On a regular basis, the RCT values of the residual feed mixtures are not only too high, but also their metal contents are too high to be applied without treatment as feeds in the above-mentioned catalytic conversion processes. The product obtained in the process according to the invention is an atmospheric residue purified from bitumen or a mixture of a vacuum distillate and a vacuum residue purified from bitumen, the product of which has a low metal content in addition to a low RCT value. This is largely due to the fact that the metal-containing distillation residue, which is subjected to bitumen removal by dissolution, has been catalytically hydrotreated. In this case, the bitumen removal of these metal-containing residues by dissolving has its own very high metal removal selectivity.

ίο 78496

Examples of bituminous hydrocarbon mixtures which can be used as feeds in the process according to the invention are: a) atmospheric residue obtained by distillation of crude mine-5 crude oil, b) vacuum residue obtained by distillation of crude mineral oil, c) asphalt bitumen separated from d) ) asphalt bitumen separated by dissolving the residues obtained by distillation of a hydrotreated residual fraction of crude mineral oil, e) mixtures of two or more of the heavy hydrocarbon mixtures mentioned in a) to d), 15 f) heavy crude oils, g) oil shale extracts, heavy extracts and i) mixtures of one or more of the bitumen-rich hydrocarbon mixtures mentioned in a) to h) with one or more low bitumen or non-bituminous hydrocarbon mixtures, such as an aromatic extract from lubricating oil production or a catalytic cracking slurry oil.

As bituminous hydrocarbon mixtures that can be used as feed in the process of the invention, the following six are recommended:

Input 1

Atmospheric residue obtained by distillation of crude mineral oil.

The study has shown that the decreases in RCT values in the catalytic hydrotreating, which achieves G values corresponding to 1.5 x Gc and 2.0 x Gc, are dependent on T 1, the RCT of the atmospheric residue (b wt%). and the percentage of atmospheric residue boiling below 520 ° C (d% by weight) and are obtained from the following 35 equations (Equation 1): H 78496 Decrease in RCT value _ bc x iqO = b 51.6-0.526xd-0.115 xT1 + 2 / 55xb + 0.00115xT1xd s -r; - ± 5 (1.426-1.15x10 JxT · ^ (1-0, Olxd) where c is the RCT value of the atmospheric residue in the hydrotreated product with an initial boiling point of T ^ ° C.

Feed 2 10 Vacuum residue obtained by distillation of crude mineral oil.

The study has shown that the decreases in RCT values in the catalytic hydrotreating to give G values corresponding to 1.5 x Gc and 2.0 x Gc depend on the value Tj, the RCT value of the vacuum residue (b% by weight) and vacuum at the boiling point of 5% by weight of the residue (Τς ° 0 and are obtained from the following equation (Equation 2): bc Decrease in RCT value = —g— x 100 = 20 73.5-0, 108xT ^ + 2.55xb-0.05xT5 - —- ± 5 1.4-1.08x10 JxTx where c is the RCT value of the atmospheric residue in the hydrotreated product with an initial boiling point of T1 ° C.

25 Input 3

Asphalt bitumen separated by dissolving crude mineral oil from the distillation residue.

The study has shown that the decreases in RCT values in the catalytic hydrotreating to achieve G-ar-30 vo corresponding to 1.5 x Gc and 2.0 x Gc depend on the value of T 1, the RCT of bituminous bitumen (b wt%) and the average molecular weight (M) of asphalt bitumen and are obtained from the following equation (Equation 3):

B-C

Decrease in RCT value = —g— x 100 = -48.5-0.108xT ^ + 32.1xlog M + (18.6-5.36xlog M) xb --- ± 5 1.4-1.08x10 ΔχΊ1 35 i2 78496 where c is the RCT value of the atmospheric residue in the hydrotreated product having an initial boiling point of T ^ ° C.

Input 4

A mixture of atmospheric residue obtained by distillation of 5 crude mineral oil and asphalt bitumen separated by dissolving bitumen from a residue obtained by distilling a hydrotreated residual fraction of crude mineral oil containing less than 50 parts by weight per atmospheric weight of asphalt.

10 The study has shown that the decreases in RCT values in the catalytic hydrotreating to give G values corresponding to 1.5 x Gc and 2.0 x Gc depend on 1) the temperature T ^, 2) the atmospheric residue (b% by weight) RCT, 15 3) the weight percentage of atmospheric residue boiling below 520 ° C (f% by weight), 4) the RCT value of asphalt bitumen (c% by weight) and 5) the asphalt bitumen / atmospheric residue-mixing ratio of the feed mixture expressed as parts by weight asphalt 100 per 20 parts by weight of atmospheric residue (r parts by weight) and are obtained from the following equation (Equation 4)::: de Decrease in RCT value = —r— = 100 = d P1'8x (91-0,9xf-2,55xb ) + (1-P) (118-1.18xf) 3.00 ------ 25 (1.426-1.15x10-3xT1 + 1.25x10_3xr) (1-0, Olxf) + 5 x 100 + r where P = 100 x b_ 100 100 xb + rxcd = RCT value of the feed mixture and 30 e = RCT value of the atmospheric residue in the hydrotreated product with an initial boiling point Tj ° C.

Input 5

Vacuum residue mixture obtained by distillation of crude mineral oil and asphalt bitumen separated by dissolving bitumen from a residue obtained by distilling a hydrotreated residue fraction of crude mineral oil containing less than 50 parts by weight of asphalt per 100% by weight of asphalt .

The study has shown that the decreases in RCT values in the catalytic hydrotreating to give G values corresponding to 1.5 x Gc and 2.0 x Gc depend on 1) the temperature T ^, 2) the vacuum residue (b% by weight) The RCT value, 3) the boiling point (T5 ° C) of 5% by weight of the vacuum residue, 10 4) the RCT value of the asphalt bitumen (c% by weight) and 5) the asphalt bitumen / vacuum residue mixing ratio of the feed mixture expressed as parts by weight per asphalt bitumen vacuum residue (r parts by weight)? and they are obtained from Equation (Formula 5): 15 Decrease in RCT value = —χ- x 100 = d 1nn_ P1'8x (66.5-2.55xb + 0.05xT5) + 118x (1-P) _ 100 + r • 5 _-5 ± 5 X 100 '1,4-1.08x10 JxT2 + 1,4x10 Jxr „„ „100 xb 20 where P = ττττί-1 — r- J 100 xb + rxcd = RCT value of the feed mixture and e = RCT value of the atmospheric residue in the hydrotreated product with an initial boiling point Tj ° C.

25 Input 6

Mixture containing bituminous bitumen I separated by dissolving bitumen from a residue obtained by distilling crude mineral oil and bituminous bitumen II separated by dissolving bitumen from a residue obtained by distilling less crude mineral oil than hydrotreated ice 50 parts by weight of asphalt bitumen II 100 parts by weight of asphalt bitumen I.

The study has shown that the reductions in RCT values in the catalytic hydrotreating to give G values corresponding to 1.5 x Gc and 2.0 x Gc depend on: i4 78 496 1) temperature Tp 2) weight of asphalt bitumen I (b -%) of the RCT value, 3) of the average molecular weight (M) of the asphalt bitumen I, 4) of the RCT value of the asphalt bitumen II (c% by weight), and 5 5) of the asphalt bitumen II / asphalt bitumen I mixture ratio expressed as parts by weight asphalt II per 100 parts by weight of asphalt bitumen I (r parts by weight); and are obtained from Equation (Equation 6): rl - 0 Decrease in RCT value = x 100 = a 10 100- P1 'βχΖΐ88,5-32, lxloq M- (18,6-5,36xloq M) xfa> 7 + lllx (1-P) 1,4-1.08x10-3xT ^ + 1,4x10_3xr, P 0 100 + r „100 xb + 5.2 x ——, nossa P = -r -; - '100' J 100 xb + rxc 15 d = RCT value of the feed mixture and e = RCT value of the atmospheric residue in the hydrotreated product with an initial boiling point of Ti ° C.

The average molecular weight M of the asphalt bitumen I 20 used as feed part in feed 6 and the average molecular weight of the asphalt bitumen used in feed 3 are determined according to ASTM method D 3592-77 using toluene as solvent.

Equations 1 to 6 above make it possible to determine whether, in view of the maximum acceptable G value (corresponding to 2.0 x Gc), it is possible to prepare, by catalytic hydrotreating alone and using feeds 1 to 6, a product which can be distilled to give an atmosphere, having an initial boiling point of T ^ ° C and a given RCT-30 value of a weight percent. If this is not possible according to the equations and thus the combined procedure has to be used and the equations still give the limits between which, in the catalytic hydrotreating of the combined process, the reductions in RCT values have to be chosen to achieve optimum efficiency in 35 combined processes.

is 78496

Feeds 4-6 consist of two mixed ingredients. One of these mixing components (mixing component I) is selected from the group consisting of atmospheric residues from the distillation of crude mineral oil, vacuum residues obtained by distillation of crude mineral oil and asphalt bitumens separated by dissolving bitumen residues. The second mixing component (mixing component II) is asphalt bitumen separated by dissolving the bitumen from the residue obtained by distilling the hydrotreated residual fraction of crude mineral oil. Examples of the latter residual fractions are atmospheric fractions and vacuum fractions obtained by distilling crude mineral oil and asphalt bitumen separated by dissolving bitumen from these residues.

A very interesting embodiment of the process according to the invention, using one of feeds 4-6, is one in which the mixing component II used as part of the feed for the first stage is asphalt bitumen obtained by removing bitumen by dissolving in the second stage. The conditions for achieving the desired reduction in RCT in the first step of the process using asphalt bitumen recycling can be determined as follows. The equation found is used to determine the reduction in RCT applied in the catalytic hydrotreating to achieve optimum efficiency in the combined process when feed component I is the only feed used. The rate through the catalyst used for this purpose is determined by several catalytic hydrotreating experiments 30 using feed component I as the feed. At this rate, the combined process produces an oil having the desired RCT value of a weight percent and an initial boiling point T 1 of the desired bitumen and asphalt bitumen (asphalt). obtained as a by-product. The found equation is then used to determine the reduction in RCT used in the catalytic hydrotreating to achieve optimum efficiency in the combined process when the ratio of mixture of mixing component I and asphalt bitumen A is desired r and is used as feed. The rate used for this purpose through the catalyst is determined by several catalytic hydrotreating experiments using a mixture of mixing component I and asphalt bitumen A as feed. Using this flow rate, the combined process produces an oil having the desired RCT value of a weight percent and an initial boiling point of T 1 ° C, and asphalt bitumen (asphalt bitumen B) is obtained as a by-product. These tests are repeated, if desired, once or several times, in each case using asphalt bitumen isolated in the previous test series, as a mixing component for mixing component I (with constant values of r) in the following test series until isolated asphalt bitumens are obtained in two successive test series. whose RCT values are substantially the same. In this way, the flow rate through the catalyst required to apply the process of the invention to the recycling of asphalt bitumen is determined. Generally, two or three sets of experiments are sufficient to give a permanent state.

The invention is further illustrated by the following examples.

Example 1 Two atmospheric residues obtained by distillation of crude mineral oils (atmospheric residues A and B) were used in the study.

Atmospheric residue A had an RCT of 10% by weight (determined according to ASTM method D 524), a vanadium content of nickel 30 of 70 ppm and a boiling percentage of less than 520 ° C of 50% by weight.

Atmospheric residue B had an RCT of 15.6% by weight (determined according to ASTM method D 524), a vanadium and nickel content of 500 ppm and a boiling point of 29.4% by weight below 520 ° C.

17 78496

In examining whether, taking into account the maximum permissible G value, it is possible, from atmospheric residue A, to produce by purely catalytic hydrotreating a product which can be distilled to give an atmospheric residue with an initial boiling point of 370 ° C and an RCT value lower than that of atmospheric residue A RCT, applying Equation 1 in the form 10 TT x 100 to Fmax (where Fmax is the maximum value of the term to the right of the equation) with parameter values b = 10, T = 370 and d = 50, it can be seen that this can be achieved very easily if the atmospheric residue to be prepared is having an initial boiling point of 370 ° C, an RCT value (c) greater than 3.6% by weight. This means, for example, that starting from atmospheric residue A, in the preparation of an atmospheric residue having an initial boiling point of 370 ° C and an RCT value (c) of 4.5% by weight, purely catalytic hydrotreating is sufficient.

However, if atmospheric residue A is to be used to make an oil with an initial boiling point of 370 ° C and a significantly reduced RCT value of 1,5% by weight, catalytic hydrotreating alone is not sufficient in view of the maximum permissible G value. In this case, in addition to the catalytic hydrotreatment, solvent removal of the bitumen must be applied. When applying Equation 1 in the form: maximum decrease in RCT = Fmax and minimum decrease in RCT = Fm ^ n 30 (where Fmax and Fm ^ n are the maximum and minimum values in the right-hand term of the equation, respectively) using the positions b = 10, T = 370 and d = 50, it turns out that for optimal use of the compound process, care must be taken to ensure that the reduction in RCT in the catalytic hydrotreatment is 54.1-64.1%.

ie 7 8 4 96

To prepare atmospheric residues with an initial boiling point of 370 ° C and different RCT values (c), atmospheric residue A was subjected to catalytic hydrotreating in thirteen experiments. The experiments were performed in a 1000 milliliter-5 reactor containing two solid catalyst layers with a total volume of 600 ml. The first catalyst layer consisted of a Ni / V / SiO 2 catalyst containing 0.5 parts by weight of nickel and 2.0 parts by weight of vanadium per 100 parts by weight of silica. The second catalyst 10 consisted of a Co / Mo / Al 2 O 2 catalyst containing 4 parts by weight of cobalt and 12 parts by weight of molybdenum per 100 parts by weight of alumina. The weight ratio between Ni / V / SiO 2 and Co / Mo / Al 2 O 3 catalysts was 1: 3. All experiments were performed at a temperature of 390 ° C, a pressure of 125 bar with an H 2 / -15 oil ratio of 1000 Nl / kg. Different flow rates through the catalyst were used in the experiments. The results of Experiments 1-13 at 450 hours of operation are shown in Table A.

For each experiment, the table shows the flow rate used through the catalyst, the reduction in RCT achieved (lo loo) and the corresponding C4® production (calculated as a percentage by weight of the feed). Experiments 1-12 were performed in pairs, with the difference in flow rates through the catalyst between the two experiments in each pair being such that the difference in RCT reduction was about 1.0%. The table also shows the C4 ~ yield per percent decrease in RCT (G) for each experimental pair.

19 78496

Table A

Experiment Flow RCT Value Output G

No. speed 1 decrease Daino-% weight-% q.g .h · * "_” ..... ...

J ^% of the feed 5 L 1.50 31.9 0.481 1> 0.015

2 1.40 32.9 0.496 J

10 3 2.42 20.0 0.300 0.015 4 2.31 21.3 0.319 5 1.07 40.2 0.603] 15> 0.016 6 1.03 41, 1 0.617) 7 0.61 53, 5 0.901 0, 023 20 8 0.57 54.7 0.929 9 0.40 63.4 1, 164]> 0.030 10 · 0.37 64, 6 1, 200] 25 11 0.30 70, 0 1, 432]> 0.057 12 0.27 71, 1 1.495 and 30 13 0.50 59.0 1.030

Only Experiments 8, 9 and 13 are experiments according to the invention. Other experiments are comparative. As can be seen from Table A, Experiments 1-2, 3-4, and 5-6 retain a G value of 35

Essentially constant (Gc). In Experiments 7-8 and 9-10, where reductions in G values of about 54 and 64% were achieved, the G values were about 1.5 x G 2 and 2.0 x G 2, respectively.

The products obtained in the catalytic hydrotreatings according to Experiments 5, 11 and 13 were then separated by atmospheric distillation and vacuum distillation into a fraction, H2S + NH4 fraction, a C8-370 ° C atmospheric distillate, a 370-520 ° C vacuum distillate and 520 ° C + -tyhjiöjäännökseksi. The vacuum was removed from the residue with bitumen with n-butane at a pressure of 40 bar at a solvent / oil weight ratio of 3: 1 and the resulting vacuum residues purified from bi-10 were mixed with the corresponding vacuum distillates. The results (of which only Experiment 16 is an experiment according to the invention) are shown in Table B.

Table B

15 Experiment, No._14_15_16 H2-treated product from Experiment No. 5 11 13

Distillation

Yield of products calculated per 100 parts by weight per feed, parts by weight C ^ - 0.60 1.43 1.03 20 H2S + NH3 2.9 3.4 3.2

Cc-370 ° C 8.2 11.7 10.5 370-52 ° C (vacuum distillate) 56.3 58.0 58.1 520 ° C + (vacuum residue) 33.3 27.7 28.9

RCT value of vacuum distillate,% by weight 0.4 0.3 0.3 25 RCT value of vacuum residue,% by weight 15.4 8.8 13.6

Bitumen removal West temperature, ° C 120 129 133

Yield of vacuum residue purified from bitumen, parts by weight 21.6 22.1 21.8 3q Yield of asphalt bitumen, parts by weight 11.7 5.6 7.1

RCT value of vacuum residue purified from bitumen,% by weight 4.4 4.6 4.8

Blend

Yield of vacuum distillate and vacuum residue purified from bitumen, parts by weight 77.9 80.1 79.9 35 Initial boiling point of the mixture, ° C 370 370 370

RCT value of the mixture,% by weight 1.5 1.5 1.5 21 78496

Applying Equation 1 in the form: K— g - x 100 = F k max ^ using the positions b = 15.6, T = 370 and d = 29.4, it turns out that it is entirely possible to prepare an atmospheric residue with an initial boiling point of 370 ° C and an RCT value lower than the RCT value of atmospheric residue B, the product 10 obtained by catalytic hydrotreating and distillation, provided that the RCT value (c) of the atmospheric residue to be produced is greater than 4.7% by weight.

However, if atmospheric residue B is to be used to produce an oil with an initial boiling point of 370 ° C and a much reduced RCT value of 2.5% by weight, catalytic hydrotreating alone is insufficient in view of the maximum permissible G value. In this case, in addition to the catalytic hydrotreating, the bitumen removal step by dissolution must be used. When applying Equation 1 in the form: maximum RCT value reduction = F and max 20 minimum RCT value reduction = F.

mm using the positions b = 15.6, T = 370 and d Ä 29.4, it appears that for optimal use of the combined process, care must be taken to ensure that the reduction in the catalytic hydro-treatment is between 60.0 and 70.0%.

If it is desired to prepare an oil having an initial boiling point of 370 ° C and an RCT value of 2.5% by weight, atmospheric residue B is subjected to a catalytic hydrotreatment of this atmospheric residue B as described in Experiments 1-13 using the same catalysts. The reaction conditions were slightly different, i. temperature 395 ° C, pressure 150 bar, flow rate through the catalyst 1.05 g / g / l and an oil / oil ratio of 1000 Nl / kg. The reduction in RCT was 65%. The product of the catalytic hydrotreating was isolated as described above by sequential atmospheric distillation and vacuum distillation 35 into several fractions. Bitumen was removed from the 520 ° C + vacuum residue with n-butane at 115 ° C, 40 bar 22 78496 with a solvent / oil weight ratio of 3: 1 and the resulting bitumen-purified vacuum residue was mixed with vacuum distillate. The results of Experiment 17 of the present invention are shown below.

5 Test 17

Distillation

Yield of products calculated per 100 parts by weight of feed 10, parts by weight 0.98 H 2 S + NH 4, parts by weight 1.5 ° C -370 ° C, parts by weight 14.2 370-520 ° C (vacuum distillate), parts by weight 48.3 520 ° C + (vacuum residue), parts by weight 32.6 15 RCT value of vacuum distillate,% by weight 0.5

RCT value of vacuum residue,% by weight 12.9

Bitumen Remover

Yield of vacuum residue purified from bitumen, parts by weight 26.8 2Q Yield of asphalt bitumen 5.8

RCT value of vacuum residue purified from bitumen,% by weight 6.1

Blend

Yield of a mixture of vacuum distillate and vacuum residue purified from bitumen 75.1 25 Initial boiling point of the mixture, ° C 370

RCT value of the mixture,% by weight 2.5

Example 2 In this example, two vacuum residues were used: (i) vacuum residue A with an RCT of 19% by weight 30 (determined according to ASTM method D 524), a vanadium and nickel content of 160 ppm and a boiling point of 5% by weight at 500 ° C, and (ii) vacuum residue B having an RCT value of 11% by weight (determined according to ASTM method D 524), a vanadium and nickel content of 20 ppm and a boiling point of 5% by weight of 520 ° C.

23 78496

Vacuum residue A cannot be used to produce an oil with an initial boiling point of 370 ° C and an RCT value of 2.5% by weight, taking into account the maximum permissible G value, by catalytic hydrotreating alone. Thus, in addition to the hydrotreatment of catalyst 5, bitumen removal by dissolution must be used.

When applying Equation 2 in the form: t

Maximum RCT value reduction = F and

max J

minimum RCT value reduction = F.

mm 10 (where Fmax and Fmin are the largest and smallest values of the right-hand term of the equation, respectively) using the positions b = 19, T ^ = 370 and T ^ = 500, it appears that for optimal use of the combined method, care must be taken to reduce the RCT in the catalytic hydrotreating-15 is between 52.0-62.0%.

To prepare atmospheric residues with an initial boiling point of 370 ° C and different RCT values (c), vacuum residue A was subjected to catalytic hydrotreating in thirteen experiments as described in Experiments 1-13 using the same catalysts at the weight ratios shown. The reaction conditions were: Temperature 385 ° C, pressure 150 bar and H 2 / oil ratio 1000 Nl / kg. Different flow rates through the catalysts were used in the experiments. The results of the tests after 18-30,500 operating hours are shown in Table-25 in size C.

Table C

Experiment Flow rate Decrease in RCT value C ^ output G value No. gg- .h "1%% of feed Weight ~% 18 0.91 30.5 0.801 | 30 19 0.87 31.5 0.828 J 0.027 20 1.36 20.0 0.525 1

21 1.30 21.2 0.557 J

22 0.60 39.9 l, 06lT 0/028 35 23 0.58 41.1 1.096 \ 24 7 8 4 96

Table C (continued)

Experiment No. Decrease in flow RCT value C4 ~ output G value speed%% of feed weight% gg “.h” 1 5 24 0.38 51.5 1.4667 25 0.36 52.4 1.502J 0 / 040 26 0.26 61.8 1.983 7 27 0.24 62.5 2.021] 0.054 28 0.17 70.0 3.0157 10 29 0.15 71.1 3.139 J 0.113 30 0.30 57.0 1.700

Only Experiments 25, 26 and 30 are experiments according to the invention.

15 Other experiments are comparative. As can be seen from Table C, in Experiments 18-19, 20-21, and 22-23, the G value remains essentially constant (Gc). Experiments 24-25 and 26-27, which showed reductions in RCT of about 52 and 62%, respectively, had a G value of about 1.5 x G and 2.0 x G, respectively. In the catalysts of Experiments 22, 28 and 30

the products obtained in the hydrotreatings were separated by sequential atmospheric distillation and vacuum distillation into several fractions as described above. Bitumen was removed from the vacuum residues with n-butane and the vacuum residue thus purified from bitumen was mixed with the corresponding vacuum distillate. The results of these experiments, of which only Experiment 33 is an experiment according to the invention, are shown in Table D. Table D

Experiment No. 31_32_33 30 H 2 treated product from Experiment No. 22 28 30

Distillation

Yield of products calculated per 100 parts by weight per feed, parts by weight C4 ~ 1.06 3.02 1.70 H2S + NH3 3.8 5.1 4.5 35 C5-370 ° C 5.8 10.0 8, 330-520 ° C (vacuum distillate) 23.5 39.0 34.0

Table D (continued)

Experiment No.____ 31_32_33 25 78496 520 ° C + (vacuum residue) 67.1 45.2 53.0

RCT value of vacuum distillate,% by weight 0.4 0.4 0.4

RCT value of the vacuum residue,% by weight 15.2 10.3 13.2

Bitumen removal Temperature, ° C 137 125 133

Yield of 10 vacuum residues purified from bitumen, parts by weight 41.0 36.2 38.0

Yield of asphalt bitumen, parts by weight 26.1 9.0 15.0

RCT value of vacuum residue purified from bitumen,% by weight 3.7 4.8 4.4 15 Mixing

Yield of vacuum distillate and vacuum residue purified from bitumen, parts by weight 64.5 75.2 72.0

Initial boiling point of the mixture, ° C 370 370 370

RCT value of the mixture,% by weight 2.5 2.5 2.5 20

Vacuum residue B alone cannot be used to produce an oil with an initial boiling point of 370 ° and an RCT of 3% by weight by catalytic hydrotreating, taking into account the maximum permissible G-value. In addition to catalytic hydro-25 treatment, bitumen removal by dissolution must be used. Application of Equation 2 in the form: maximum decrease in RCT = F and

max J

minimum decrease in RCT value = F. t min indicates that for optimal use of the combination process, care must be taken to ensure that the reduction in the catalytic hydrotreating is between 30.6 and 40.6%.

Vacuum residue B was subjected to catalytic hydrotreating to produce an oil having an initial boiling point of 370 ° C and an RCT of 3.0% by weight. Experiment 34 was performed in a 1000 ml reactor containing 600 ml volume of the same Co / Mo / Al 2 O 3 catalyst used in Example 1. The reaction conditions were: temperature 390 ° C, pressure 125 bar, flow rate through the catalyst 1.0 μg / μh 1 and Hj / oil ratio 1000 Nl / kg. From the 520 ° C vacuum residue obtained after vacuum distillation of the catalytic hydrotreating product, bitumen was removed with n-butane at 127 ° C, 40 bar and a solvent / oil weight ratio of 3: 1, and the resulting bitumen-purified vacuum residue was mixed with a 370-520 ° C vacuum distillate. The results of the experiment of this invention are shown below.

Experiment No. 34

Distillation

Yield of products calculated per 100 parts by weight per feed, parts by weight 15 C4 ~ 1 '* H2S + NH3 1.0 C5-370 ° C 3.5 370-520 ° C (vacuum distillate) 20.6 520 ° C + (vacuum residue) 71.2 20 RCT value of vacuum distillate, 0.3% by weight

RCT value of the vacuum residue, percentage by weight 9.1

Bituminpolsto

Yield of vacuum residue purified from bitumen, parts by weight 56.0 25 Yields of asphalt bitumen, parts by weight 15.2

RCT value of vacuum residue purified from bitumen,% by weight 4.0

Blend

Yield of vacuum distillate and vacuum residue purified from bitumen, parts by weight 76.6 30 Initial boiling point of the mixture, ° C 370

RCT value of the mixture, 3.0% by weight

Example 3

In the following experiments, two asphalt bitumens were used.

35 Asphalt bitumen A was obtained by removing bitumen from a vacuum residue of crude mineral oil with propane. It had an RCT value of 27 78496 of 25.4% by weight (calculated from the CCT value determined according to ASTM method D 189), an average molecular weight of 1400 (determined according to ASTM method D 3592/77 using toluene as solvent) and vanadine + nickel content 250 ppm (by weight).

Asphalt bitumen B was obtained by removing the bitumen with n-butane from the vacuum residue of crude mineral oil. It had an RCT value of 48.0% by weight (calculated from the CCT value determined according to ASTM method D 189), an average molecular weight of 2000 (determined according to ASTM method D 8592/77 using toluene as solvent) and vanadium + nickel content 420 ppm.

Catalytic hydrotreating alone is not sufficient for the production of asphalt bitumen A oil with an initial boiling point of 370 ° C and an RCT value of 3.0% by weight, taking into account the maximum permissible G value. Thus, in addition to catalytic hydrotreating, bitumen removal by dissolution must be used. When applying Equation 3 in the form: maximum RCT decrease = F ^ and max 20 minimum RCT decrease = F.

It appears that for optimal use of the combined process, care must be taken to ensure that the reduction in RCT in the catalytic hydrotreating is between 51.0 and 61.4%.

Asphalt bitumen A was subjected to catalytic hydro-25 treatment in thirteen experiments to produce atmospheric residues with an initial boiling point of 370 ° C and different RCT values (c). The experiments were similar to those in Experiments 1-13, however, the weight ratio between Ni / V / SiO 2 and Co / Mo / Al 2 O 2 catalysts was 1: 2. The reaction conditions were: a temperature of 40 ° C, a pressure of 145 bar and an oil / oil ratio of 1000

Nl / kg as well as variable flow rates through the catalysts were used. The results of experiments 35-46 at 450 operating hours are shown in Table E.

35 28 78496

Table E

Experiment Flow rate RCT C. output G-value No. g.g-1.h ”1 decrease% of feed weight%

S

35 0.61 30.2 1.054 '0.030 36 0/58 31.3 1.087 10 37 0.91 19.8 0.689 0.030 38 0.88 20.7 0.716 * 39 0.40 39.8 1.390] 15 0.032 40 0 .38 41.0 1.428 41 0.27 50.8 1.880) 0.044 20 42 0.25 51.7 1.920 «43 0.18 60.6 2.528 • 0.060 44 0, 17 61.8 2.600 25 '45 0.11 70.5 3.996 0.212 46 0.10 71.5 4.208 30 47 0.22 56.0 2.220

Only Experiments 42, 43 and 47 are experiments according to the invention. Other experiments are comparative. As can be seen from Table E, in Experiments 35-36, 37-38, and 39-40, the G value remains essentially unchanged (G). Experiments 35 c sa 41-42 and 43-44 showed a decrease in RCT values 29 78496

set about 51 and 61%, respectively, had a G value of about 1.5 x G

and 2.0 x G, respectively, c

The products obtained in the catalytic hydrotreatings according to Experiments 39, 45 and 47 were separated into separate fractions by sequential atmospheric distillation and vacuum distillation. Bitumen was removed from the 520 ° C + vacuum residues with n-butane and the resulting bitumen-purified vacuum residues were mixed with the corresponding 370-520 ° C vacuum distillates. The results are shown in Table F, where experiment 10 is in accordance with the invention.

Table F

Experiment No._48_49_50 I ^ treated product from Experiment No. 39 45 47 15 Distillation

Yield of products calculated per 100 parts by weight per feed, parts by weight C4 "1.39 4.00 2.22 H2S + NH3 3.0 4.0 3.4 20 C5-370 ° C 13.9 19.4 17, 0 370-520 ° C (vacuum distillate) 13.2 22.0 18.4 520 ° C (vacuum residue) 70.0 53.1 61.0

RCT value of vacuum distillate,% by weight 0.5 0.3 0.4

RCT value of vacuum residue, 25% by weight 18.1 10.5 14.5

Temperature Temperature, ° C 132 130 130

Yield of vacuum residue purified from bitumen, parts by weight 39.8 41.9 41.5

Yield of asphalt bitumen, weight-30 parts 30.2 11.2 18.5

RCT value of vacuum residue purified from bitumen,% by weight 3.8 4.4 4.2

Mixture „Yield of vacuum distillate and purified vacuum residue of bitumen, parts by weight 53.0 63.9 59.9 30 78496

Table F (continued)

Experiment # 48_49_50

Initial boiling point of the mixture, ° C 370 370 370

RCT value of the mixture,% by weight 3.0 3.0 3.0 5 Catalytic hydrotreating alone is not sufficient for the production of asphalt bitumen B oil with an initial boiling point of 370 ° C and an RCT value of 4% by weight, taking into account the maximum permissible G value. In addition to the catalytic hydrotreatment, bitumen removal by dissolution must be used.

10 When applying Equation 3 in the form: maximum decrease in RCT value = F and

max J

minimum reduction in RCT = F min it appears that for optimal use of the combination process, care must be taken to ensure that the reduction in RCT in the catalytic hydrotreating is between 56.1 and 66.5%.

Asphalt bitumen B was subjected to a catalytic hydrotreating to produce an oil having an initial boiling point of 370 ° C and an RCT of 4.0% by weight. The experiment was similar to experiments 1-13 with a weight ratio of Ni / V / SiO 2 and 20 Co / Mo / Al 2 O 2 catalysts of 1: 1. The reaction conditions were: temperature 390 ° C, pressure 150 bar, flow rate through the catalysts 0.41 g / g / H 2 O / oil ratio 1000 Nl / kg. The decrease in RCT was 61.0%. The 520 ° C + vacuum residue of the catalytic hydrotreating product was then stripped of bitumen with n-butane at 120 ° C, 40 bar and a solvent / oil weight ratio of 3: 1, and the resulting bitumen-purified vacuum residue was mixed with a 370-520 ° C vacuum distillate. The results of the experiment according to the invention are shown in the following.

Experiment No. 51 Distillation

Yield of products calculated per 100 parts by weight per feed, parts by weight C ~ 3.7 35 4 H2S + NH2 6.1 ¢ ,, - 370 ^ 19 »9

D

31 78496 370-520 ° C (vacuum distillate) 17.0 520 ° C + (vacuum residue) 55.6

RCT value of vacuum distillate,% by weight 0.6 5 RCT value of vacuum residue,% by weight 24.2

Bitumen Remover

Yield of vacuum residue purified from bitumen, parts by weight 33.9 10 Yield of asphalt bitumen, parts by weight 21.7

RCT value of vacuum residue purified from bitumen, 5.7% by weight

Blend

Yield of a mixture of vacuum distillate and bituminous vacuum residue, wt. 50.9 15 Initial boiling point of the mixture, ° C 370

RCT value of the mixture, 4.0% by weight

Example 4 An AB mixture obtained by mixing 100 parts by weight of atmospheric residue A and 20 parts by weight of asphalt bitumen B was used in this experiment. The RCT value of the atmospheric residue was 9.8% by weight (determined according to ASTM method D 524), its vanadium and nickel concentration of 95 ppm and boiled at a temperature below 520 ° C for 50% by weight. The asphalt bitumen B had an RCT value of 25 to 35% by weight (calculated from the CCT value determined according to ASTM method D 189) and a vanadium and nickel content of 110 ppm. Asphalt bitumen B was obtained by removing bitumen with n-butane from a vacuum residue obtained by distilling a vacuum residue from a hydrotreated mineral oil.

Catalytic hydrotreating alone is not sufficient to produce an AB mixture with an initial boiling point of 370 ° C and an RCT of 1.5% by weight, taking into account the maximum permissible G-value. Thus, in addition to catalytic hydrotreatment, bitumen removal by dissolution must be used.

32 78496

When applying Equation 4 in the form: maximum decrease in RCT = F and

max J

the minimum decrease in RCT · '= F. „c min using the positions b = 9.8, c = 35, r = 15, T ^ = 370 ^ and f = 50 it is observed that for optimal use of the combination method, care must be taken that The reduction in RCT in the catalytic hydrotreating is between 34.6 and 46.2%.

The AB mixture was subjected to catalytic hydrotreating in eleven experiments to prepare atmospheric residues with an initial boiling point of 370 ° C and different RCT values (e). The experiments were similar to those shown in Experiments 18-30, but with a weight ratio of Ni / V / SiO 2 and Co / Mo / AlO 2 catalysts of 1: 2.5. Reaction conditions were: temperature 385 ° C, pressure 150 bar and oil / oil ratio 1000 Nl / kg and different flow rates through the catalyst were used. The results of Experiments 52-62 after 425 hours of operation are shown in Table G.

33 78496

Table G

Experiment No. Flow rate RCT value C. ”- return G value -1, -1 decrease4-„ ...... ....

gg .h%% of feed% by weight 5 52 5.31 10.1 0.217 0.021 53 4, 84 11, 0 0.236 10 54 2.09 22.3 0.475 '0.022 55 2.02 23.1 0.493 56 1.19 34, 2 0.838 1 15 and 0.032

57 1.13 35.4 0.876 J

58 0.68 46, 1 1.280 0, 042 20 59 0.65 47, 0 1.318 60 0.41 60.3 2.057 0.086 61 0.40 61.8 2, 168 25 62 0.86 40 ', 5 1.030 + Decrease in RCT value χ 100% d 30 Only experiments 57, 58 and 62 are experiments according to the invention. Other experiments are comparative. As can be seen from Table G, in Experiments 52-53 and 54-55, the G values remain substantially constant (G). In experiments 56-57 v and 58-59, which resulted in reductions in RCT values of about 35 35 and 47%, respectively, G values were about 1.5 x G and 2.0 x G, respectively. c c 34 73496

The products obtained in the catalytic hydrotreatings according to Experiments 54, 60 and 62 were separated by successive atmospheric distillation and vacuum distillation into separate fractions, and bitumen n-butane was removed from the 520 ° C + vacuum residues under normal conditions. The results (where only experiment 65 is an experiment according to the invention) are shown in Table H.

Table H

^ Experiment No._63_64_65 i ^ treated product from Experiment No. 54 60 62

Distillation

Yield of products calculated per 100 parts by weight per feed, parts by weight 15 C ~ 0.5 2.1 1.0 H2S + NH3 1.6 3.1 2.8 C5-370 ° C 9.5 14.0 12, 3,370-520 ° C (vacuum distillate) 43.7 50.1 48.8 520 ° C + (vacuum residue) 45.2 32.0 36.1 20 RCT value of the vacuum distillate,% by weight 0.4 0.3 0.3

RCT value of the vacuum residue,% by weight 19.7 12.9 17.9

Bitumen removal Temperature, ° C 137 132 133 25

Yield of vacuum residue purified from bitumen, part by weight 22.0 22.4 21.8

Yield of asphalt bitumen, parts by weight 23.2 9.6 14.3

RCT value of vacuum residue purified from bitumen,% by weight 3.7 4.2 4.2 ^ Mixing

Yield of a mixture of vacuum distillate and vacuum residue purified from bitumen, parts by weight 65.7 72.5 70.6

Initial boiling point of the mixture, ° C 370 370 370 35 RCT value of the mixture,% by weight 1.5 1.5 1.5

Three additional experiments (Experiments 66-68) were performed to produce an oil with an initial boiling point of 370 ° C and an RCT-35 78496 value of 1.5% by weight. In the experiments, three different residual feeds were subjected to catalytic hydrotreating in the reactor used in Examples 1-13 and using the same reaction conditions and catalysts at the weight ratios indicated therein. The products of the catalytic hydrotreating were further treated as described in Experiments 14, 15 and 16.

Experiment 66 The feed used in this experiment was atmospheric residue C. Atmospheric residue C was obtained by distillation of crude mineral-10 oil, had an RCT of 10% by weight (determined according to ASTM method D 524) and a vanadium and nickel content of 70 ppm and boiled below 520 ° C 50 by weight. When applying Equation 4 in the form: maximum RCT decrease = F and max 15 minimum RCT decrease = F.

It appears that for optimal use of the combined process, care must be taken to ensure that the reduction in RCT in the catalytic hydrotreating is between 54.1 and 64.1%. In the catalytic hydrotreating of Experiment 66, the flow rate through the catalyst was 0.50 g / g and the reduction in RCT was 59%. In the bitumen removal of Experiment 66, asphalt bitumen D with an RCT value of 41% by weight was separated by dissolution.

Experiment 67 The feed used in this experiment was a CD mixture obtained by mixing 100 parts by weight of atmospheric residue C with 12 parts by weight of asphalt bitumen D obtained in Experiment 66 above.

When applying Equation 4 in the form of: 30 largest decrease in RCT value = F and

max J

minimum decrease in RCT value = F.

It was found that for optimal use of the combined process, care must be taken to ensure that the reduction in RCT in the catalytic hydrotreating is between 36.5 and 47.7%. In the catalytic hydrotreating of Experiment 67, the flow rate of 36 78496 through the catalyst was 0.43 g.g / h ^ and an RCT reduction of 42.1% was achieved. Upon removal of the bitumen by dissolution, asphalt bitumen E with an RCT value of 39% by weight was separated. Experiment 68 5 The feed used in this experiment was a mixture of CE obtained by mixing 100 parts by weight of atmospheric residue C with 12 parts by weight of asphalt bitumen E obtained in Experiment 67 above.

When applying Equation 4 in the form: 10 largest decrease in RCT value = F and max minimum decrease in RCT value = F.

It appears that for optimal use of the combined process, care must be taken to ensure that the reduction in RCT in the catalytic hydrotreating is between 37.1 and 48.3%. The flow rate through the catalysts used in the catalytic hydrotreating of Experiment 68 was 0.43 μg and the reduction in RCT achieved was 42.7%. Upon removal of the bitumen, asphalt bitumen F with an RCT value of 39% by weight was separated by dissolution. the value 20 is the same as that of the asphalt bitumen E, this is the point at which the process has reached its stationary state when the asphalt bitumen is recycled.The results of Experiments 66-68 are shown in Table I.

Table I

^ Experiment No. 66 67 68

Distillation

Yield of products calculated per 100 parts by weight per feed, parts by weight 3Q C4 "1.03 0.92 0.93 H2S + NH3 3.2 3.0 3.0 C5-370 ° C 10.5 9.8 9, 9,370-520 ° C (vacuum distillate) 58.1 51.9 52.0 520 ° C + (vacuum residue) 28.9 36.1 35.9 35 RCT value of the vacuum distillate,% by weight 0.3 0.3 0, 3 78496

Table I (continued)

Experiment #66___67___68

RCT value of vacuum residue,% by weight 13.6 18.3 17.9

Bitumen removal Temperature, ° C 133 135 136

Yield of vacuum residue purified from bitumen, part by weight 21.8 21.6 21.8

Yield of asphalt bitumen, parts by weight 7.1 14.5 14.1 10 RCT value of vacuum residue purified from bitumen% by weight 4.3 4.4 4.3

RCT value of asphalt bitumen,% by weight 41 39 39

Blend

Yield 15 of a mixture of vacuum distillate and vacuum residue purified from bitumen, parts by weight 79.9 73.5 73.8

Initial boiling point of the mixture, ° C 370 370 370

RCT value of the mixture,% by weight 1.5 1.5 1.5

Example 5 A heavy mixture AB obtained by mixing 100 parts by weight of vacuum residue A and 30 parts by weight of asphalt bitumen B was used. The RCT value of vacuum residue A was 19% by weight (determined according to ASTM method D 524), vanadium + nickel content 180 ppm and a 5% boiling point of 520 ° C. The RCT value of the asphalt bitumen B was 35% by weight (calculated from the CCT value determined according to ASTM method D 139) and the vanadium + nickel content was 110 ppm. It was obtained by removing bitumen from n-butane from a vacuum residue obtained by distilling a hydrocarbon-treated mineral oil residue.

Catalytic hydrotreating alone is not sufficient to prepare an oil from mixture AB with an initial boiling point of 370 ° C and an RCT value of 2.5% by weight, taking into account the maximum permissible G value. In addition to the catalytic hydrotreating, bitumen removal by dissolution must be used. When applying Equation 5 in the form: 38 78496 maximum RCT value reduction = F and max minimum RCT value reduction = F.

It appears that for optimal use of the combined process, care must be taken to ensure that the reduction in RCT in the catalytic hydrotreating is between 34.0 and 47.0% by weight.

Mixture AB was subjected to catalytic hydrotreating in eleven experiments to produce atmospheric residues with an initial boiling point of 370 ° C and variable RCT values (e). The experiments were similar to those shown in Experiments 1-13, however, the weight ratio between the Ni / V / SiO 2 and Co / Mo / Al 2 O 2 catalysts was 1: 2. The reaction conditions were: temperature 380 ° C, pressure 170 bar and oil / oil ratio 1000 Nl / kg and varying flow rates through the catalyst were used. 15 The results of experiments 69-79 after 400 hours of operation are shown in Table J.

For each experiment, the table gives the flow rate used, the decrease in RCT x 100 ^, and the corresponding C ^ yield (calculated as a percentage by weight of the feed). Experiments 20 69-78 were performed in pairs, with the difference in flow rate between the two experiments in each pair being such that the difference in RCT reduction was about 1.0%.

The table further shows the C ^ yield per percent decrease in RCT (G) for each pair of experiments.

25 39 7 Q / Q £

Table J

Experiment No. Flow rate RCT value C ^ -, yield G value g, g .h decrease "*"% of feed weight% ____% _ 69 2.95 10.2 0, 380 0, 037 70 2'69 11, 1 0.413 y 10 71 1.16 22.4 0.832) f 0.038 72 12 23.2 0.860 j 15 73 0.66 33.5 1.410 0.056 n 0.63 34.3 1.454; 75 0.38, 46.8 2.240 20 0.074 76 0.36 - 47.7 2.306 77 ° '23 '58.5 3.370 25 °' 125 78 0.22 59.3 3.470 79 0.48 40.8 1,800 de 20 + Decrease in RCT value = x 100%

Only Experiments 74, 75 and 79 are experiments according to the invention. Other experiments are comparative. As can be seen from Table J, in Experiments 69-70 and 71-72, the G value remained essentially constant (Gc). In experiments 73-74 and 25 75-76, which resulted in reductions in RCT values of about 34 and

47%, respectively, G values were 1.5 x G, respectively

c and 2.0 x Gc.

78496 40

The catalytic hydrotreating products of Experiments 71, 77 and 79 were further treated as described above for Experiments 14, 15 and 16. The results (where only Experiment 82 is an experiment according to the invention) are shown in Table 5 K.

Table K

Experiment No. 80_81_82 ^ treated product from Experiment No. 71 77 79

Distillation 10 Yield of products calculated per 100 parts by weight of feed, parts by weight C4 “0.8 3.4 1.8 H2S + NH3 2.2 4.1 3.5 C5-370 ° C 8.0 12.8 11 375-520 ° C (vacuum distillate) 22.9 32.0 29.4 520 ° C (vacuum residue) 67.2 49.9 55.8

RCT value of vacuum distillate,% by weight 0.4 0.3 0.3

RCT value of vacuum residue,% by weight 23.5 15.2 20.3

Bitumen removal 20 Temperature, ° C 134 130 131

Yield of vacuum residue purified from bitumen, parts by weight 30.4 33.9 32.4

Yield of asphalt bitumen, parts by weight 36.8 16.0 23.4

RCT value of the vacuum residue purified from bitumen,% by weight 4.1 4.6 4.5

Blend

Yield of a mixture of vacuum distillate and vacuum residue purified from bitumen, parts by weight 53.3 65.9 61.8

Initial boiling point of the mixture, ° C 370 370 370

RCT value of the mixture,% by weight 2.5 2.5 2.5

Example 6

Three experiments (Experiments 83-85) were performed to prepare an oil with an initial boiling point of 370 ° C and an RCT of 2.5% by weight and to investigate the applicability of 1.1 78496 recycling of asphalt bitumen prepared by catalytic hydrotreating. In three experiments, different residual feed materials were subjected to catalytic hydrotreating in the same reactor and using the same reaction conditions as shown in Experiments 18-30. The products from the catalytic hydrotreating were further treated as described in Experiments 14, 15 and 16.

Experiment 83 The feed used in this experiment was the vacuum residue A of Example 5. The application of Equation 5 shows that for optimal use of the combined process, care must be taken to ensure that the reduction in RCT in the catalytic hydrotreating is between 52 and 62%. In the catalytic hydrotreating of Example 83, the flow rate through the catalyst was 0.30 g / g and the reduction in RCT achieved was 57%. In the removal of bitumen from Experiment 83 by dissolution, asphalt bitumen C with an RCT value of 36% by weight was separated.

Experiment 84 The feed used in this experiment was a mixture AC obtained by mixing 100 parts by weight of vacuum residue A 20 with 20 parts by weight of asphalt bitumen C obtained in the above experiment 83. The application of Equation 5 shows that for optimal use of the compound method, care must be taken to that the reduction in RCT in the catalytic hydrotreating is between 38.4 and 50.4%. The flow rate through the catalyst used in the catalytic hydrotreating of Example 84 was 0.29 g / hr and a reduction in RCT of 45% was achieved. Upon removal of the bitumen by dissolution, asphalt bitumen D with an RCT value of 39% by weight was separated.

Experiment 85 30 The feed used in this experiment was a mixture AD obtained by mixing 100 parts by weight of vacuum residue A with 20 parts by weight of asphalt bitumen D obtained in the above experiment 84. Applying Equation 5, it was necessary to take care of the combined method. that the reduction in RCT in the catalytic hydrotreating is between 37.8 and 49.8 I. The flow rate through the catalyst used in the catalytic hydrotreating of Experiment 42 78496 85 was 0.28 μg and the reduction in RCT achieved was 44%. . Upon removal of the bitumen by dissolution, asphalt bitumen E with an RCT value of 5 of 39% by weight was separated. Since the RCT value of the asphalt bitumen E is the same as the RCT value of the asphalt bitumen D, this is the point at which the process has reached a stationary state in the recycling of the asphalt bitumen. The results of Experiments 83-35 are shown in Table L.

10

Table L

Experiment #83_84_85

Distillation

Yield of products calculated per 100 parts by weight per feed, 15 parts by weight C4 "1.70 1.56 1.58 H2S + NH3 4.5 3.9 3.9 C5-370 ° C 8.3 7.4 7, 230-520 ° C (vacuum distillate) 34.0 30.1 29.9 20 520 ° C + (vacuum residue) 53.0 58.5 58.7

RCT value of vacuum distillate,% by weight 0.4 0.4 0.4

RCT value of the vacuum residue,% by weight 13.2 18.0 18.7

Bitumen removal ^ Temperature, ° C 133 133 132

Yield of vacuum residue purified from bitumen, part by weight 38.0 35.1 34.6

Yield of asphalt bitumen, parts by weight 15.0 23.4 24.1

RCT value of the vacuum residue purified from bitumen,% by weight 4.4 4.3 4.3

RCT value of asphalt bitumen,% by weight 36 39 39

Blend

Yield of a mixture of vacuum distillate and vacuum residue purified from bitumen, 35 parts by weight 72.0 65.2 64.7

Initial boiling point of the mixture, ° C 370 370 370

RCT value of the mixture,% by weight 2.5 2.5 2.5 * 3 78496

Example 7 A heavy mixture AB obtained by mixing 100 parts by weight of asphalt bitumen A and 35 parts by weight of asphalt bitumen B was used. The RCT value of asphalt bitumen A obtained by removing bitumen from propane from a vacuum residue was 25.4% by weight (calculated Of the CCT value determined according to ASTM method D 189), vanadium + nickel content 250 ppm and average molecular weight 1400. The RCT value of asphalt bitumen B was 40% by weight (calculated from the CCT value determined according to ASTM method D 189) and vanadium + nickel kelium concentration 125 ppm. It was obtained by removing the bitumen by dissolving in n-butane from a vacuum residue obtained by distilling hydrotreated asphalt bitumen, the latter asphalt bitumen was obtained by removing the bitumen by dissolving the mineral oil in a vacuum residue.

Catalytic hydrotreating alone is not sufficient to produce an oil from mixture AB with an initial boiling point of 370 ° C and an RCT value of 3.0% by weight, taking into account the maximum permissible G value. In addition to the catalytic hydrotreatment, bitumen removal by dissolution must be used. Applying Equation 6, it appears that for optimal use of the combined process, care must be taken to ensure that the reduction in RCT in the catalytic hydro-25 treatment is between 36.7 and 50.7%.

The residual feed mixture AB was subjected to catalytic hydrotreating in eleven experiments to prepare atmospheric residues having an initial boiling point of 370 ° C and varying RCT values (e). The experiments were similar to those shown in Experiments 18-30, however, the weight ratio between Ni / V / -SiCl 2 and Co / Mo / Al 2 O 2 catalysts was 1: 2. All other reaction conditions were the same. The results of Experiments 86-96 after 430 hours of operation are shown in Table M.

35 ^ 78496

Table M

Experiment No. Flow rate RCT value C. output G value -1, -1 decrease „..... .... 0 μg .h%% of feed% by weight 5 86 1.29 10.2 0.226 0, 022 87 1.18 11.1 0.246, 10 88 0.62 20.4 0.468 0.023 89 0.60 21.7 0.489, 90 0.34 36.3 0.894 1 15 j 0.033

91 0.32 37, 4 0.930 J

92 0.19 50.5 1, 427 0.044 20 93 0.18 51, 3 1.462 94 0.11 65.6 2.295 0.072 95 0.10 66.5 2.360 _ 25 96 0.25 43.5 1.150

Only Experiments 91, 92 and 96 are experiments according to the invention. Other experiments are comparative. As can be seen from Table M of M, in Experiments 86-87 and 88-89, the G values remain substantially constant (G). In Experiments 90-91 and 92-93, which achieved RCT reductions of about 37 and 51%, respectively, the G-values were about 1.5 x Gc and 2.0 x Gc> 35, respectively, in the catalytic hydrotreatings of Experiments 89, 94 and 96. the products obtained were further processed as described in Experiments 14, 15, 16 of 145 73496. The results (where only Experiment 99 is in accordance with the invention) are shown in Table N.

Table N

5 Experiment No._____97_98_99 I ^ treated product from Experiment No. 89 94 96

Distillation

Yield of products calculated per 100 parts by weight per feed, parts by weight C4 "0.5 2.3 1.1 H2S + NH3 2.0 4.2 3.5 C5-370 ° C 9.1 14.7 13.2 370-520 ° C (vacuum distillate) 18.2 24.2 22.7 520 ° C + (vacuum residue) 71.2 57.6 61.3

RCT value of vacuum distillate,% by weight 0.3 0.3 0.3

RCT value of vacuum residue,% by weight 28.7 14.1 22.5

Bitumen removal Temperature, ° C 131 130 128 20

Yield of vacuum residue purified from nitumen, part by weight 29.4 38.4 34.0

Yield of asphalt bitumen, parts by weight 41.8 19.2 27.3

RCT value of vacuum residue purified from bitumen,% by weight 4.7 4.7 4.7 25 Mixing

Yield of a mixture of vacuum distillate and vacuum residue purified from bitumen, parts by weight 47.6 62.6 56.7

Initial boiling point of the mixture, ° C 370 370 370

RCT value of the mixture,% by weight 3.0 3.0 3.0 30

Example 8

Two experiments were performed to prepare an oil with an initial boiling point of 370 ° C and an RCT value of 3.0% by weight and to investigate the feasibility of recycling asphalt bitumen formed in catalytic hydrotreating. In these experiments, two different residual feeds were subjected to a catalytic hydrotreatment in a 1000 ml reactor containing two solid catalyst layers with a total volume of 600 ml. The catalyst layers consist of the same Ni / V / SiO 2 and Co / Mo / Al 2 Og catalysts. however, a weight ratio of 1: 2 was used in Example 1. The reaction conditions were: temperature 400 ° C, pressure 145 bar and H 2 / oil ratio 1000 Nl / kg The products of the catalytic hydrotreating were further treated as in Experiments 14, 15 and 16 are shown.

Experiment 100 The feed used in this experiment was the asphalt bitumen A of Example 7. Applying Equation 6, it appears that for optimal use of the combined process, care must be taken to ensure that the reduction in RCT in the catalytic hydrotreating is between 51.0 and 61.4%. The flow rate through the catalyst used in the catalytic hydrotreating of Experiment 100 was 0.22 g / g and the reduction in RCT achieved was 56%. Asphalt bitumen C with an RCT value of 36 was found to be 36% by weight in the removal of bitumen from the experiment.

Experiment 101 The feed used in this experiment was a mixture of AC obtained by mixing 100 parts by weight of asphalt bitumen A with 25 parts by weight of asphalt bitumen C obtained in Experiment 100 above. Applying Equation 6, it must be ensured that The reduction in the value in the catalytic hyarc treatment is between 41.0 and 54.0%. The flow rate used in the catalytic hydrotreating of Example 101 through the catalyst was 0.21 g / g and the reduction in RCT achieved was 47.5%. Asphalt bitumen D with an RCT value of 36 p ainoj ·?:. ··· cents was denied in the bitumen removal by dissolution.

Since the RCT value of the asphalt bitumen D is the same as the RCT value of the asphalt 35 bitumen C, this is the point where the process has reached a stationary state of 1.7 78496 when the asphalt bitumen is recycled. The results of Experiments 100 and 101 are shown in Table O:

Table O

Experiment No. 100_101 5 Distillation

Yield of products calculated per 100 parts by weight of feed, parts by weight C4 ~ 2.22 2.0 H2S + NH3 3.4 2.9 10 C5-370 ° C 17.0 14.4 370-520 ° C (vacuum distillate) 18.4 16.0 520 ° C + (vacuum residue) 61.0 66.7

RCT value of vacuum distillate,% by weight 0.4 0.4

RCT value of vacuum residue,% by weight 14.5 17.9 15 Bitumen removal Temperature, ° C 132 133

Yield of vacuum residue purified from bitumen, part by weight 41.5 38.0

Yield of asphalt bitumen, parts by weight 19.5 28.7

RCT value of vacuum residue purified from bitumen,% by weight 4.2 4.1

RCT value of asphalt bitumen,% by weight 36 36

Blend

Yield of a mixture of vacuum distillate and vacuum residue purified from bitumen, 2 g by weight 59.9 54.0

Initial boiling point of the mixture, ° C 370 370

RCT value of the mixture,% by weight 3.0 3.0

Example 9 A heavy mixture ABC was obtained, which was obtained by mixing 30 parts by weight of 55 parts by weight of atmospheric residue A with 30 parts by weight of vacuum residue B and 15 parts by weight of asphalt bitumen C. The RCT value of atmospheric bitumen A obtained by distillation of crude mineral oil was 10 weight percent (determined according to ASTM method 524), vanadium + nickel 35 with a kelium content of 70 ppm and a boiling percentage below 520 ° C of 148 78496 percent by weight. Vacuum residue B, obtained by distillation of crude mineral oil, had an RCT value of 20.6% by weight (calculated from the CCT value determined according to ASTM method D 189), vanadium 5 nickel content 170 ppm and 5% boiling point 500 ° C. Asphalt bitumen C was obtained by removing the bitumen with propane by dissolving the mineral oil in a vacuum residue.

It had an RCT value of 25.4% by weight (calculated from the CCT value determined according to ASTM method D 189-10 ti), an average molecular weight of 1400 (determined according to ASTM method D 3592-77 using toluene as solvent) and a vanadium + nickel content of 250 ppm.

The mixture had an ABC RCT of 15.5 wt%, a vanadium + nickel content of 127 ppm and 29.5 wt% of the alloy boiled below 520 ° C.

The mixture ABC having an RCT value of 15.5% by weight (b) was subjected to catalytic hydrotreating in fifteen experiments to produce atmospheric residues with an initial boiling point of 370 ° C and RCT values (c) of 20 different. The experiments were similar to those shown in Examples 1-13, however, the weight ratio between the Ni / V / SiO 2 and Co / Mo / Al 2 O 2 catalysts was 1: 2. The reaction conditions were: temperature 400 ° C, pressure 160 bar and oil / oil ratio 1500 Nl / kg and variable flow rates through the catalysts were used. The results of Experiments 102-116 after 250 hours of operation are shown in Table P.

1.9 78496

Table P

Experiment No. Flow rate RCT value output G value -1, -1 decrease „..... .... G „g.g .h ^% of feed% by weight 5 102 11.4 10.4 0.166) 1 0.016 103 10, 4 11.3 0.181

'J

104 6.05 19.8 0.312 10 0.016 105 5.62 21, 0 0.331 106 2.62 39, 7 0.652)> 0.017 15 107 2.53 40.6 0.668] 108 1, 69 50.2 0.836 0.018 109 1 , 61 51.5 0.859 20 110 1.13 59.9 1.037 1 0.024 111 1.08 60.9 1.061 / 25 112 0, 70 70.2 1.316 0.032 113 0.67 70.9 1.339 ^ 114 0.37 80 , 1 1.908) 30 j 0.131 115 0.35 81.1 2.039] 116 0.90 65.0 1.165 50 78496

Of experiments 102-116, only experiments 111, 112 and 116 are experiments according to the invention. Other experiments are comparative. As can be seen from Table P, in Experiments 110-111 and 112-113, which achieved reductions in RCT values of about 60 and 70%, respectively, the G value was about 1.5 x G and 2.0 x G, respectively.

c J c

The product of the catalytic hydrotreating of Experiment 116 was separated by sequential atmospheric distillation and solvent removal of bitumen as described above. The results are shown below.

Experiment No. 117 I-treated product from Experiment No. 116

Distillation 15 Yield of products calculated per 100 parts by weight of feed, parts by weight C4 “1/17 H2S + NH3 2.2 C5-370 ° C 13.3 2Q 370-520 ° C (vacuum distillate) 47.0 520 ° C + ( vacuum residue) 33.9

RCT value of vacuum distillate,% by weight 0.5

RCT value of vacuum residue,% by weight 12.5

Bitumen removal ^ „Yield of vacuum residue purified from bitumen, parts by weight 2 7.6

Yield of asphalt bitumen, part by weight 6.3

RCT value of vacuum residue purified from bitumen, 5.8% by weight

Mixture 30 Yield of a mixture of vacuum distillate and bitumen-purified vacuum residue, 74.6 parts by weight

Initial boiling point of the mixture, ° C 370

RCT value of the mixture, 2.5 parts by weight Solvent = n-butane; solvent / oil weight ratio = 3: 1; 35 temperature = 118 ° C; pressure = 41 bar.

Claims (10)

A process for preparing a hydrocarbon mixture having an RCT value of α% by weight and an initial boiling point of 5 DEG C., in which the bituminous hydrocarbon mixture is subjected to a catalytic hydrotreating to reduce its RCT value, the product obtained is separated by distillation to atmospheric distillate C, wherein either the bitumen-purified atmospheric-10 residue having the desired RCT value of a by weight is obtained from said atmospheric residue by removing the bitumen by dissolving, or the atmospheric residue is first divided by distillation into vacuum distillate and vacuum residue from which the asphalt bit The RCT value is such that, when this latter vacuum residue purified from bitumen is mixed with said vacuum distillate, a mixture having the desired RCT value of a% by weight is obtained, characterized in that the catalytic hydro-treatment is carried out under conditions which The percentage yield of C has been performed under mild conditions. Process according to Claim 1, characterized in that a catalyst containing at least one metal which is nickel or cobalt and, in addition, at least one metal which is mol-lybdenum or tungsten on a support is used in the catalytic hydrotreating to reduce the RCT value. , which supports more than 40% by weight of alumina. Process according to Claim 2, characterized in that a catalyst consisting of a metal combination of nickel-molybdenum or cobalt-molybdenum using alumina as support is used in the catalytic hydrotreating to reduce the RCT value. 52 78496 Process according to Claim 2 or 3, characterized in that the vanadium / nickel content of the bituminous hydrocarbon mixture is greater than 50 ppm (by weight) and that in the catalytic hydrotreating this mixture is contacted with two successive catalysts, the first catalyst being a demetallizing catalyst. , which contains more than 80% by weight of silica, and the second catalyst is a catalyst used to lower the RCT value, as set forth in claim 2 or 3. Process according to Claim 4, characterized in that the demetallization catalyst consists of a nickel / vanadium-metal combination using silica as support. Process according to one of Claims 1 to 5, characterized in that the catalytic hydrotreating is carried out at a temperature of 300 to 500 ° C, a pressure of 50 to 300 bar, with a flow rate through the catalyst of 0.02 to 10 μg. with a feed ratio of 20,100 to 5,000 Nl / kg. Process according to Claim 6, characterized in that the catalytic hydrotreating is carried out at a temperature of 350 to 450 ° C at a pressure of 75 to 200 bar, a flow rate through the catalyst of 0.1 to 2 μg and a feed ratio of 500 to 450 μg. 2000 Nl / kg. Process according to one of Claims 1 to 7, characterized in that the removal of the bitumen by dissolution is carried out on the vacuum residue of the hydrotreated product. Process according to one of Claims 1 to 8, characterized in that the removal of the bitumen by dissolution is carried out using n-butane as solvent at a pressure of 35 to 45 bar and a temperature of 100 to 150 ° C. 53 7 8 4 9 6 Process according to one of Claims 1 to 9, characterized in that the asphalt bitumen separated in the step of removing the bitumen by dissolving from the residue obtained by distilling the hydrotreated residual fraction of crude mineral oil is used as a mixing component in the first stage feed. 54 7 8 4 9 6