DE1470504B - Process for the production of specialty or white spirit - Google Patents

Description

The invention relates to the production of specialty or white spirits by catalytic treatment of a straight-run petroleum gas under equilibrium pressure auto-financing conditions.

Special and boiling point petrol and white spirit are well-known petroleum products. Special and special boiling point petrol usually boil in the range of 30 to 150 ° C and white spirits in the range of 150 to 200 ° C. Both must be negative in the doctor test and have a good odor and good odor resistance exhibit. As a further requirement, their aromatics and olefin content must be low. you will be normally made from straight-run gasolines, either by acid treatment or by hydrofining (i.e. catalytic desulfurization in the presence of added hydrogen) have been refined.

Another suitable refining process is auto refining, which is particularly beneficial in cases where hydrogen is not readily available. The car refining of gasoline is the subject of the British Patent 654 152, and the auto refining of kerosene and white spirit is in the British Patent 669,536. As the aromatic content in specialty and special boiling point spirits and mineral spirits must be low, there is minimal aromatics formation during auto refining he wishes. This is achieved when the autofining treatment is performed at equilibrium pressure as described in British Patent 697,083.

The auto-refining catalysts must be used for the formation of hydrogen be able to dehydrate naphthenes in aromatics, albeit this dehydrogenation reaction from the previously indicated Reasons should be kept at a minimum amount. The catalysts must still be able to be to hydrogenate organic sulfur compounds. They must also be used against sulfur compounds, present in the reaction zone, be persistent. Usually cobalt- and molybdenum oxides on aluminum oxide are used, but it has now been found that noble metal catalysts are also used can be used.

The invention accordingly relates to a process for the production of specialty or white spirit with a negative doctor test, acceptable odor and good odor stability due to catalytic treatment one boiling in the range from 30 to 200 ° C and containing 0.01 to 1 percent by weight sulfur, where appropriate, straight-run petroleum gas subjected to removal of the excess sulfur Equilibrium Pressure Autofining Conditions, which is characterized in that in the presence a reforming catalyst is worked, which is a platinum group metal on a refractory oxide contains as a carrier.

For the process according to the invention, catalysts are used which are normally used for the catalytic reforming of petroleum hydrocarbons are needed. These catalysts contain preferably 0.01 to 5 percent by weight, in particular 0.1 to 1 percent by weight, of the platinum group metal. Platinum is preferably used as the platinum group metal. That which serves as a carrier Refractory oxide is preferably aluminum oxide, optionally with a small proportion of an acidic one activating component, e.g. B. 1 to 40 percent by weight, preferably 3 to 15 percent by weight, Silicic acid or 0.1 to 8 percent by weight, preferably 0.1 to 2 percent by weight, fluorine and / or chlorine. During the autofining process, sulfur compounds are present in the reaction zone. It has it has been shown that the catalysts work properly under these conditions. Preferably removed however, the hydrogen sulfide formed is removed from the hydrogen-rich gas which is returned to the reaction zone. This can for example by treatment with a sulfur-absorbing solid or with a selective solvent, z. B. with an amine solution, as used in the known Girbotol process, can be achieved. the Sulfur content in the feedstock going into the autofining zone is between 0.01 and 0.1 percent by weight, in particular between 0.01 and 0.05 percent by weight. According to a particularly preferred one Embodiment of the method according to. of the invention, feedstocks, their sulfur content is higher than stated above, subjected to treatment prior to autofining by which * the excess sulfur is removed. This can be done in a simple manner by treating the feedstock done with a solid adsorbent, such as natural or activated Clay or bauxite. This treatment can be carried out at room flow velocities (calculated as a liquid) from 0.1 to 4.0 V / V / hour, at temperatures in the range from 288 to 371 ° C and at pressures of Normal pressure up to 3.5 atmospheres can be carried out.

Removal of some of the sulfur before the autofining treatment has a change in the Equilibrium pressure-temperature relationship and enables, for example, the application a higher equilibrium pressure at a given temperature or a lower temperature at a given equilibrium pressure. The hydrogenation is carried out by higher pressures and / or lower Temperatures favored, and it can be assumed that this is the case with the. improved results plays a role. Obtaining products that are negative in the doctor test and have a good odor and Having good odor resistance is not only made easier, but it may also be possible to get on to dispense with a subsequent redistillation. The amount of sulfur removed depends on the sulfur content of the feed and on the activity of the Catalyst. . .

When operating under equilibrium pressure autofining conditions, the temperature is normally in the range from 208 to 438 ° C, in particular from 371 to 427 ° C, and the pressure im Range from 7 to 42 atmospheres, in particular from 17.5 to 35 atmospheres. The space flow velocity can be between 0.1 and 10 V / V / hour and is preferably 2 to 5 V / V / hour.

The process according to the invention can be carried out in a conventional reforming plant operating with platinum catalysts can be carried out without significantly changing the system. It is suitable especially for implementation in the earlier reforming plants that work under mild conditions and are provided with devices for circulating gas scrubbing. It has also been shown that catalysts which have been used extensively for reforming, as catalysts for the process are suitable according to the invention. For example, in one case the results were good with a

Catalyst obtained which contained 0.3 percent by weight of platinum and with which 96 m ^{3 of} gasoline per kilogram of catalyst had already been reformed to an RON of 80.

As already mentioned, it is possible under certain circumstances to switch to the usual subsequent redistillation to refrain from removing a small amount of produce, but the products can then be fractionated into special and white spirits with the desired boiling limit ranges are broken down. The suitability of the products can be assessed in the usual way to be determined. The sulfur content is usually determined by the doctor test, which must be negative, and the odor and odor stability determined by comparison with a reference sample.

For example
Production of specialty and boiling point petrol

An experiment was carried out in a plant that was normally used for reforming with platinum catalysts and comprised the following parts: a pre-fractionation for the feedstock, three reforming reactors connected in series, which contained a platinum-alumina-halogen catalyst with 0.3 weight percent platinum and 0, Contained 7 percent by weight halogen (0.35 percent by weight fluorine and 0.35 percent by weight chlorine), a separator for reactor products 30, and cycle gas and a column for product stabilization. The cycle gas was washed with amine to remove hydrogen sulfide and then with glycol to remove water in a conventional Girbotol system. The catalyst had already been used in a normal catalytic reforming plant to increase the RON of gasoline to 80, with 96 m ^{3 of} gasoline per kilogram of catalyst being put through. A straight-run gasoline was used as the feedstock, which, after pre-fractionation, gave a reactor feed which had a boiling range from 33 to 169 ° G (ASTM distillation) and contained 0.067 percent by weight sulfur. The feed was subjected to the autofining treatment by passing it through the reactor system under the equilibrium pressure conditions given in Table 1. A stabilized, doctor test negative liquid product with a sulfur content of 0.0022 percent by weight was obtained. The stabilized product was broken down in a customary continuous distillation into specialty and special boiling point petrol with the following boiling ranges: 60/90, 80/110 and 100/140. Each fraction had the same odor as a corresponding comparison sample that met the quality requirements. The odor of each product was stable during storage. The key figures for the use of the reactor, the stabilized product and the special boiling point spirits are given in Table 1 below.

Table 1

Operating conditions:

_{Reactor temperature} , ° C 410 Ö5

Reactor pressure, atü 17.5

Space velocity,
V / V / h 3.0

Circulation gas amount, m ³ / m ³ 450

Hydrogen content of the cycle gas, percentage by volume 93

Key figures of the reactor use and the stabilized
Product:
Specific weight at

15 ° / 4 ° C

ASTM distillation:

Initial boiling point, ⁰ C

5%, ° C

10%, ° C

50%, ° C

90%, ⁰ C

95%, ° C

End of boiling point, ⁰ C,.

Doctor test ..:

Total sulfur, weight percent

Olefins, volume percentage ...
. Aromatics, percent by volume

mission

0.7050

33

50

58

104

145

155

169

0.061 0.5

4.5

product

0.7118

39

56

62 103 144 152 171 negative

0.0022

0.5

6.5

60/90 Boiling range 100/140 80/110 Redistilled Boiling limit benzjne: specific weight 0.6755 0.7360 at 1574 ° C 0.7090 ASTM distillation: 58 103 Beginning of boiling, ⁰ C ... 79 83 137 End of boiling, ⁰ C 0.5 108 0.5 Olefins, percent by volume 0.5 Aromatics, volume 0.5 8.5 percent 2.0 Odor comparison with Comparative samples that the quality requirements same same correspond stable same stable Stability of the odor. stable

B e i s ρ i e 1 2 Manufacture of special boiling point petrol

Another attempt was made in the catalytic reforming plant described in Example 1 accomplished. In this experiment, the raw gasoline was partially desulphurized before the pre-fractionation, by being at 328 ° C, a space velocity (in terms of liquid state) of 0.8 V / V / hour and a pressure of 1.75 atü was passed through a column, the granulated bleaching earth contained. In doing so, the sulfur content of the crude feed became 0.065 percent by weight reduced to 0.014 weight percent. This feedstock was then given the autofining treatment under the equilibrium pressure conditions shown in Table 2 subject. The stabilized product from the auto-fining treatment was at the Doctor's

test negative and contained 0.0001 weight percent sulfur. Special boiling point spirits obtained by fractionating the stabilized product had the same odor as corresponding comparison samples which met the quality requirements and were odor-stable. The ratios of reactor feed and refined products are given in Table 2 below. A comparison of the results of Examples 1 and 2 shows that with prior desulfurization of the reactor insert a much higher Autofmierungs equilibrium pressure is obtained at the same operating temperature (30 atm compared to 17.5 atm at 41O ⁰ C) and that desulfurized with the previously Use a higher throughput of 4.3 V / V / hour. compared to 3.0 V / V / h was possible.

Table 2

Operating conditions:

Reactor ^{temperature, 0} C 410

Reactor pressure, atü, 30

Space velocity,

V / V / hr 4.3

Circulation gas volume, m ³ / m ³ 600

Hydrogen content of the cycle gas,
Volume percentage 98

mission product Properties of the reactor insert and stabilized Product: specific weight at 15 ° / 4 ° C - 0.7135 0.7175 ASTM distillation: Initial boiling point, ⁰ C 47 55 5%, ⁰ C 64 69 10%, ⁰ C 70 '74 50%, ⁰ C 104 106 90%, ° C 138 142 95%, ⁰ ° C 149 150 End of boiling, ⁰ C 158 160 Doctor test negative Total sulfur, Weight percent 0.014 *) 0.001 Olefins, volume percentage ... 0.5 0.5 Aromatics, percent by volume 6.0 6.5

*) The use was from 0.065 to 0.014 percent by weight Sulfur content is desulfurized by being heated at 329 ° C, 0.8 V / V / hour. and 1.75 atm was passed over activated fuller's earth.

ς 60/90 > iedbereich 100/140 80/110 Redistilled Boiling limit gasoline: specific weight • at 15 ° / 4 ° C ASTM distillation: 62 102 Beginning of boiling, ⁰ C ... 80 82 138 End of boiling, ⁰ C 106 Olefins, 0.5 0.5 Volume percentage 0.5

Aromatics,

Volume percentage

Odor comparison with
Comparative samples that
the quality requirements

correspond

Stability of the odor.

60/90

Boiling range
80/110

0.5

same
stable

1.5

same
stable

100/140

equally stable

Example 3
Production of white spirit

In the catalytic reforming plant described in Example 1, an experiment was carried out in which a straight run gasoline containing 0.148 weight percent sulfur passed through the fuller's earth column was performed to obtain a reactor insert containing 0.072 percent by weight sulfur. This feed was subjected to the autofining treatment under equilibrium pressure conditions, a stabilized product was obtained which was negative in the doctor test, 0.0002 percent by weight and had the same odor as a corresponding comparative sample containing the Quality requirements met. The odor of the product was stable during storage. Working conditions and the properties of the reactor feed and the stabilized product are below given in Table 3.

Table 3
Operating conditions:

Reactor ^{temperature, 0} C 795

Reactor pressure, atü 30

Room flow velocity,

V / V / hr 3.0

Circulation gas volume, m ³ / m ³ 890

Hydrogen content of the cycle gas,
Volume percentage 97

Properties of the reactor insert and the stabilized one
Product:

specific weight

at 15 ^O / 4 ^O C ..... 0.7775 0.7785

ASTM distillation:

Initial boiling point, ⁰ C 150.5 153

5%, 157 157 ° C

10%, ⁰ C: ... 158.5 158.5

50%, 166 ° C 166

90%, ° C 177 177.5

95%, ° C 182 182.5

End of boiling, ° C 188 200

Doctor test positive negative

Total sulfur,

Weight percent 0.072 *) 0.0002

*) The feed material was desulphurized from 0.148 to 0.072 percent by weight of sulfur by adding at 343 ° C, 0.6 V / V / h. and 1.75 atm was passed over activated fuller's earth.

mission

product

continuation

mission product Olefins, volume percentage ... 0.5 1.0 Aromatics, percent by volume 18.0 19.5 Odor comparison with Comparative samples that the quality requirements correspond same Stability of the odor - stable

Example 4

Another attempt was made in the catalytic reforming plant described in Example 1 carried out in which a straight-run gasoline containing 0.115 weight percent sulfur in the lead stove tower was treated, with a reactor insert with a sulfur content of 0.034 percent by weight was obtained. The reactor feed was autofinished treatment under equilibrium pressure conditions subjected to a stabilized product was obtained that negative in the doctor test was, contained 0.0001 weight percent sulfur and had the same odor as a comparative sample a corresponding test gasoline that met the quality requirements. The smell of the product was stable during storage. The working conditions and the key figures of the input material and the stabilized product are shown in Table 4 below. A comparison of the results of the Examples 3 and 4 show that an autofining equilibrium pressure can be achieved by prior partial desulphurization of the reactor feed of 30 atm at a lower reactor temperature (416 versus 423 ° C) below otherwise the same operating conditions are possible.

Table 4

Operating conditions:

Reactor ^{temperature, 0} C 416

Reactor pressure, atü 30

Space velocity,

V / V / h 3.0

Circulation gas volume, m ³ / m ³ ............ 855

Hydrogen content of the circulating gas,
Percentage by volume .. '. ". 98

Properties of the reactor insert and the stabilized one
Product::

specific weight
at 1574 ° _: C. ■. '. · ■ ... ■:; ■ _. ■;.; ..
, ÄSTM distillateJon: V ■ ''. ^: ':
r -Si.edeanfang, ⁰ C ....., ..
V; .-: '57Oi ⁰ C .-.; ..: ....-: ^

End of boiling point, ⁰ C ,, .....,.

mission

0.7775

152 149 159 · · 157 161 159 Ϊ68 ^; 167 179 ·. ■■■■■ '■■■ 180 183 185 189> .194

product

0.7785

mission product Doctor test .... negative Total sulfur, Weight percent 0.034 *) 0.0001 Olefins, volume percentage ... 0.5 0.5 Aromatics, percent by volume 17.5 20.5 Odor comparison with Comparative samples that the quality requirements correspond same Stability of the odor stable

*) The feed material was desulfurized from 0.115 to 0.034 percent by weight of sulfur by adding it at 329 ° C, 0.6 V / V / h. and 1.75 atm was passed over activated fuller's earth.

B e i s ρ i e 1 5 Manufacture of special boiling point petrol

Another attempt was made in the catalytic reforming plant described in Example 1 accomplished. Before this attempt, however, the reactors were equipped with fresh platinum-alumina-halogen catalyst filled, the 0.3 percent by weight platinum and 0.7 percent by weight halogen (0.35 percent by weight Fluorine and 0.35 percent by weight chlorine). The raw starting material was before the Pre-fractionation partially desulfurized by placing it at 329 ° C, a space flow velocity (related on liquid state) of 0.6 V / V / hour. and 1.75 atm by one with granulated fuller's earth filled tower was headed. Here, the sulfur content of the raw starting material was from . 0.07 percent by weight reduced to 0.041 percent by weight. This material was listed below subjected to the equilibrium pressure conditions shown in Table 5 to the autofining treatment. The stabilized product was negative in the doctor test and contained 0.0001 percent by weight sulfur. Through Fractionation of the stabilized auto-refining product, special boiling-point spirits were obtained which had the had the same odor as corresponding comparison samples that met the quality requirements. the Key figures of the reactor use and the products obtained in the refining are below in Table 5 given. A comparison of the results of Examples 2 and 5 shows that using a a much higher car-

. Finierungs-equilibrium pressure (32.5 compared to 30 atü) at.einer operating temperature (385 compared to 41O ⁰ C) is obtained than when using the catalyst used in Example 2. .: ";:" ■■ - ■ . :::

: .... ': V ".' R '' ^V ''. \. '■■ ■' Table 5 " ^ v "'' / ''. , ^? Ϊ ~ ..Γ '. _: Operating conditions:; ^ i.: /;.·■;

Reactor temperature, ° C: ..... 400

Reactor pressure, atü 32.5

Space velocity,

V / V / hr 2.5

Circulation gas volume, m ³ / m ³ 779

Hydrogen content of the cycle gas, percentage by volume 98

009 524/227

continuation

Properties of the reactor insert and the stabilized one
Product:
specific weight

at 15 ° / 4 ° C

ASTM distillation:
Initial boiling point, ⁰ C

10%, ⁰ C
50%, ⁰ C
90%, ⁰ C

95%,

End of boiling, ⁰ C

Doctor test

Total sulfur,

Weight percent

Olefins, volume percentage ...
Aromatics, percent by volume

mission

0.717

51 -

65

72 108 147 157 180

positive

0.014 *)

6.0

product

0.720

57

70

76 109 150 165 182 negative

0.0001

8.0

*) The use was from 0.07 to 0.014 weight percent sulfur content desulfurization by at 329 ° C, 0.6 V / V / h. and 1.82 atm was passed over activated fuller's earth.

60/90 Boiling range 100/140 80/110 Redistilled Boiling limit gasoline: specific weight 0.678 0.737 at 15 ° / 4 ° C 0.7095 ASTM distillation: 60 101 Beginning of boiling, ⁰ C ... 87 79 136.5 End of boiling, ⁰ C 0 108.5 0.7 Olefins, percent by volume 0.5 Aromatics, 0.5 ⁷ ' ⁵ Volume percentage 2.0 Odor comparison with Comparative samples that the quality requirements same same correspond same

Examples Production of white spirit

Another attempt was made in the catalytic reforming plant described in Example 1 carried out, in which, however, the same fresh platinum-alumina-halogen catalyst as in Example 5 was used. The raw raw material became partial before the pre-fractionation desulfurized by it at 329 ° C, 0.6 V / V / h. (on Liquid state referred) and 1.75 atm was passed through a column, the granulated bleaching earth contained. In doing so, the sulfur content of the crude feed was increased to 0.135 percent by weight 0.047 percent by weight reduced. This material was listed in Table 6 below Equilibrium pressure conditions subjected to the autofining treatment. The stabilized product

from this treatment was negative in the doctor test, contained 0.0001 percent by weight sulfur and had the same odor as a comparison sample of a corresponding test gasoline that met the quality requirements. The working conditions and the characteristics of the starting material and the stabilized product are given in Table 6. A comparison of the results of Examples 4 and 6 shows that when using the fresh catalyst, a significantly higher equilibrium pressure (33 versus 30 atmospheres) at a somewhat lower reactor temperature (410 versus 416 ^° C.) was obtained than when using the catalyst of Example 4.

Table 6

Operating conditions:

Reactor ^{temperature, 0} C 410

Reactor pressure, atü 33 ■

Space velocity,

V / V / hr ■ .... 2.5

Circulation gas volume, m ³ / m ³ 798

Hydrogen content of the cycle gas, percentage by volume 98

Properties of the reactor insert and the stabilized one
Product:

specific weight
at 1574 ⁰ C ........,

ASTM distillation:
Initial boiling point, ° C ..,

³ C

³ C

'C-

³ C

³ C

5%,

10%,

50%,
90%,
95%,

End of boiling point, ° C

Doctor test

Total sulfur,

Weight percent

Olefins, volume percentage ...
Aromatics, percent by volume
Odor comparison with
Comparative samples that
the quality requirements
correspond

mission

0.774

146

148.

151

158

173

180

190

positive

0.047 0.5 18.0

product

0.777

152 156 157 165 182 188 199 negative

0.0001 0.5

21.5

same

Claims (5)

Patent claims: 1. A process for the production of special or test fuels with negative Doctor test, an acceptable odor and good odor stability subject by catalytically treating a to 200 ⁰ C boiling in the range of 30 and 0.01 to 1 weight percent sulfur-containing, optionally, a removal of the sulfur surplus straight- run petroleum gas under equilibrium pressure autofining conditions, characterized in that it is carried out in the presence of a reforming catalyst containing a platinum group metal supported on a refractory oxide. 2. The method according to claim 1, characterized in that in the presence of a catalyst is worked, the platinum group metal in amounts of 0.01 to 5 percent by weight, preferably 0.1 to 1 percent by weight. 3. Process according to Claims 1 and 2, characterized in that in the presence of an aluminum oxide is operated as a carrier-containing catalyst. 4. The method according to claims 1 to 3, characterized in that a starting material is the Process is subjected to its sulfur content by pretreatment with a solid absorbent has been reduced to values of 0.01 to 0.05 percent by weight. 5. The method according to claims 1 to 4, characterized in that the Autofinierungsbehandluijg at temperatures from 288 to 438 ° C, preferably 371-427 ⁰ C, and pressures of 7-42 atm, preferably 17.5 to 35 atm, is performed.