DE1930830C - High performance fuel - Google Patents

Description

Properties drawn with a heat value of the order of magnitude of 10 200 to 11000 cal / g (9000 to 10000 cal / cm ³ ), the freezing point being below -7O ^U C. The propellant also has a greater stability against oxidation and heat and a smaller proportion of such impurities as sulfur than any other common jet fuel.

The, the raw material forming aromatic oil, which results in a fuel with such excellent properties was obtained by a so-called pitch portion of a tar-like substance was removed, which has been obtained by subjecting a crude oil at a temperature above 700 ⁰ C and under 2300 In general, a heat treatment between 900 and 1500 ^° C. was particularly advantageous. If necessary, an additional heat treatment was carried out at a temperature of 250 to 550 ° C. for a period of 1 minute to 5 hours, the preferred Obtaining raw material for the fuel by removing the light components in this way, cleaving the long side chains or undergoing dealkylation, and by accelerating the aromatization. However, the higher the heat or high temperature treatment temperature, the less this process is required.

Such a tarry substance is essentially a cracked product that is used in the production of Olefins such as ethylene or in the decomposing gasification for the production of town gas as waste has been received.

The crude oil to be used in such cracking can be any gaseous hydrocarbon or a mixture thereof, any distillation oil or heavy gasoline, a kerosene or Light oil, a residual oil such as a heavy oil, or a light or heavy crude oil.

The aromatic oil, which results in the inventive fuel usually has a boiling point under normal atmospheric pressure of 200 to 450 ⁰ C and preferably a boiling point between 240 and 35O ° C. It is a mixture which consists mainly of a polycyclic aromatic component, but with regard to the splitting off of the rope chain accompanying the hydrogenation treatment it is advantageous that only a few and small side chains are present. Therefore, a particularly advantageous result is obtained with an H — C ratio of 0.5 to 1.0 and a specific gravity of 1.0 to 1.3.

The hydrogenation treatment is carried out using any conventional method, apparatus and catalyst. The treatment is therefore carried out at a pressure of ¹ O his? () () Ku im '. a temperature of 2 (Kl bi>. -ISi (. emvn disproportion of \ V; i '.- t: rsto (T.! i'oin.itisL'lu-ni ¹ M \ on S to? li i.iu ! -.:hut II ίι · - vki. it- · - l <aiim-i. ie- ehu indiiikeil \ '' ^l! '' · '"': · '- '. ''>! ■ ' ii'i'i iiu ai 1 a. ¹ - K .il.tl ·. ■ old ■:. al - '. ι · "-, -!., - JiJVa., ρ, ·;'. liurrhiH'liiiirt \ UK a! al ·. salor ν! ■ - ..: i: · I> π ".. ·. Ii kimu-aoli, de 'd.uiuieli her-

! '. ii ι '■ .:.' ■! ■ iw uik'i rille M lsi. I, Ii: i »\ <ni / uci

'; a. 'IiK-U'! ' Λ ·; Melall ·. · From de; Vi lippe \ 'l 11. u ·, . ν; = ν "i. V-KMän.! iM.ii. Kiipfu. Ki.ilieiiiii '·.

■ ■ ■ ■ ■ ·. . .! i ri in K heia um. ι '-, mi nil' 11 iiii Uli.

■ · 'i' .-. '!. ι July: - in, ii hen: a:; <we! Ai! E aiul i'.re oxides and sulfides with a carrier such as aluminum, kieselguhr, clay, activated carbon or synthetic Zeolite, is combined. The hydrogenation process can furthermore be carried out in one or more steps, depending on the reaction conditions, such as catalyst, and the raw materials, such as purification content in the raw material. It is extremely advantageous to use a conventional desulphurisation system in the first stage in order to protect the hydrogenation catalyst. In connection with such a desulfurization system, basic conditions such as a reaction temperature of 350 to 450 ° C, a pressure of 20 to 100 kg / cm ³ , a molar ratio of hydrogen / raw material of 5 to 15 and a liquid space velocity are used from 0.5 to 20. At the catalyst, cobalt-molybdenum, nickel-molybdenum or nickel-cobalt-molybdenum, attached to aluminum oxide, silicon dioxide, aluminum oxide or zeolite, is used.

The invention is described in more detail below by means of examples.

Table 1

45

5: 5

35

LHSV 1 General properties Distillation experiments: 10% distillation temperature in ⁰ C 220 50% distillation temperature in ¹ C 222 90 "/ o distillation temperature in ⁰ C 280 Elemental analysis: C in ⁰ I _n 86.1 There % 13.9 H / C 1.94 Physical Properties: Viscosity in cp at 20 ^° C 6.0 Refractive index nff 1.4870 specific weight a *. ° 0.9020 High frequency absorption spectroscopy aromatic H in% 0 aromatic side chain H in ⁰ I ₀ . 0 naphthenic H in% 68 aliphatic CH ₂ H in ° / ₀ ... 20th aliphatic CFI ₃ H in%. .. 12th Fuel oil tests Hei / value in cal / g 10 850 Hei / Wert in cal / cnv ' 9 790 existing rubber in 111 L ¹ KH) til! ¹ ... 0 ialenlei kaulsehuk in nijj. lUcnr ' ¹ 1 Be it white! in i. iev-iehlon> / enl. . . 0.002 Mcri apian-.ehwelel in ι lewichts- pr.wini 0, (K) (K) i'esamle Saul emenue in ιημ KVU I μ 0 ! ) amp; drutk üi kü em- 0.035 l \ up'ei'plaii.enkiiir '.m .m ■: 1 iiiei mi-, he Siahihi.il terrific (iel 'Ii; punk' in ' line 70

not just about his

ÄfiSS

H e i s ρ i c I 1

line void-like substance, which had been produced by the heat decomposition of petroleum spirit at 1200 ° C. for a contact time of 0.002 seconds, was subjected to fractional distillation to produce a fraction with the properties J 'at 20 ° to 330 ° C. ⁰ - 1.055, nf -1.6320, a viscosity of 29 Cp at 20 "C and a HC / Yc ratio of 0.82, namely with a distillate of 10% at a distillation temperature of 220 C, 50 % at a distillation temperature of 265 ° C. and 90% at a discharge temperature of 324 ° C. This fraction was then introduced into a through-reaction tube which was loaded with a catalyst which, in the usual way, by the addition of 30% nickel to diatomaceous earth The hydrogenation was carried out under the following conditions: WasverstoffmoKerhälinis

1.5. I lüssiiikeilsraumgeschwindigkeil 1, Keak- * <■

lion temperature from 240 to 280 C and pressure 40 kg / cm ² . The maximum water absorption was 80 l / kg. The liquid substance obtained after the completion of the epiphysis process was distilled, and a fraction having a melting point of 200 to 280 "C was collected: thereafter, measurements for determining the physical properties and the search for celiac oil were carried out. The results are shown in Table 1.

JIS K-2209 [ASTM

_Calorific values according to JIS K-2279 (ASTM D-240 | μι - _ΐηι . En with benzoic acid as a reference substance, "-er

Using a ^ P ^^ imeter ^ existing rubber JIS £ -2261 (AS! M total sulfur content. JlS K-2262 (AS 1 .1

^ Rubber JIS K-227S (ASTM I) -KT verschwelel JlS K-2535. (ASTM DI, 77 (ASlMD23K _ft ,

Gefrieipu
Copper plate corrosion KlS
/ ASTM D-130),

₃ "

; gcbcn.
As can be seen from Table 1, the invention vapor pressure is JISK-2258 (ASTM O-3? 3).

thermal stability ASTMJ) -1660.

total amount of acid JiS K-2501. .

With the 1 hole frequency / absorption spectrosc. it is difficult to determine whether de, \ | fabric of paraflin or alkyl naples. fabric is. l'ntcr taking into account the la. In index, the specific view ichtcs and the raw. Structure and infrared analysis and the mass spec: analysis it can be assumed to be correct ■.! choose that the hydrogen is mainly de · - Afkylnaphthcnischen component resulticM

is ■ -.he ser-

Table J

1. General characteristics of distillation experiments:

10% distillation temperature in ° C. .. 50% distillation temperature in ¹ C ... 90% distillation temperature in "C ...

Element analysis:

C in%

There %

H / C

Physical Properties:

Viscosity in cp at 20 "C

Refractive index hü "

specific gravity d '°

High frequency absorption spectroscopy:

aromatic H in%

aromatic side chain H in%

naphthenic hin%

aliphalic CH ₂ - II in%

aliphalic CH _; , - There %

2. Fuel oil tests

Calorific value in cal / g

Calorific value in cal / cm ³

available rubber in mg / 100 cm ³ latent rubber in mg / 100 cm ³

Sulfur in percent by weight

Mercaptan sulfur in percent by weight

total amount of acid

Copper plate corrosion

thermal stability

hydrogenated ·, oil from
Schu crtccr

2 - 2. hydrogenated ii!

off at 9 (X) ¹ T /cil.ii.-n

tar

225 215 252 247 295 289 85.9 86.2 14.0 13.8 1.9 (i 1.92 4.3 4.8 1.4685 1.4692 0.860 0.863 0 0 0 0 58 27 23 21 1 10 660 10 580 9 170 9 130
1 1
3 1
2 <0.002 -.0.002 0.0001 0.0001 0 0 -- 1
lcr excellent ^. 1
terrific

Example 2

A petroleum naphtha or mineral spirits was mixed with heated steam, heated in an external tubular reactor entered and 1.5 1 sec. Heat-treated at a temperature of 72o C and 2 ⁰ 0.5 sec. At a temperature of 920 ⁰ C. the under 1. teerförmige produced substance had a specific gravity of less than 1.0, and a HC ratio of 1.09, and considering the structure of paraffin obtained by high frequency absorption spectroscopy, it was found that it contained a considerable amount of hydrogen; it was therefore treated at 400 ° C. for 5 hours for processing. The fraction from 220 to 350 ° C of this particulate substance was collected and the properties were measured as follows.

1. d? = 1.010, nf = 1.582, viscosity at 2O ⁰ C = 3.8 Cp and HC = 1.010

2. d>. ° = 1.048, n? = 1.598, viscosity at 2O ⁰ C = - 5.2 Cp and HC - 1.048.

The above-mentioned fraction was then introduced into parallel flow-through reaction tubes which were loaded in the first stage with nickel-cobalt-aluminum oxide (3: 7:90) and in the second stage with nickel (30% by weight kieselguhr; the hydrogenation was carried out under the following conditions carried out: space flow velocity = 0.7; temperature = 350 ^° C.; hydrogen molar ratio = 15 and pressure = 100 kg / cm *. The amount of hydrogen absorption was 720 l / kg for 1. and 780 l / kg for 2. The high-boiling fraction with a boiling point above 30O ⁰ C was removed from the hydrogenated oil produced, and the general measurements were carried out to determine the properties, and also the fuel oil tests were carried out. As Table 2 shows, all of these Ergi; b-

ao nisse excellent.

Table 3

hydrogenated oil

gasified tar from

Minas crude oil

hydrogenated oil from

heat-decomposed tar from

Ceria crude oil

1. General characteristics of distillation experiments:

10% distillation ^{temperature in 0} C ...

5O ° / o Distillation temperature in ° C ...

90% distillation ^{temperature in 0} C ... • Element analysis:

C in%

There %

H / C

Physical Properties:

Viscosity in cp at 2O ⁰ C

Refractive index nf

specific weight df

High frequency absorption spectroscopy:

aromatic H in%

aromatic side chains H in% ...

naphthenic H in%

aliphatic CH ₂ - H in%

aliphatic CH ₃ - H in%

2. Heating oil tests

Calorific value in cal / g

Calorific value in cal / cm ³

available rubber in mg / 100 cm ³

latent rubber in mg / 100 cm ³

Sulfur in%

Mercaptan sulfur in%

total amount of acid

Copper plate corrosion

thermal stability

202 206 238 256 273 281 85.9 85.7 14.1 14.2 1.97 1.99 4.3 4.8 1.4685 1.4705 0.865 0.888 0 0 0 0 60 62 13th 20th 27 18th 10 850 10 800 9400 9 600 1 0 3 1 <0.002 <0.002 0.0001 0.0001 0 0 1 <1 terrific terrific

Example 3

A teerförmige substance which was obtained by decomposing and gasifying Minas crude oil at a temperature of 900 ⁰ C, was distilled and a fraction 240-350 ° C was collected. The characteristics of this fraction were as follows:

nf = 1.5962; d? = 1.002; Viscosity = 5.0 Cp 2O ⁰ C and HC = 0.96. This fraction was introduced into e Durchflußreaktionsröhre, with Kat: capacitors of tungsten sulfide and nickel sulfide, <ang annealed to an alumina support, loaded w treatment was carried out in the first stage at ei space velocity of 1.0, a T <temperature of 400 ⁰ C. and a hydrogen molar

MS

nis of 10 at a pressure of 50 kg / cm ² ; the subsequent treatment took place in the second stage at a space flow rate of 0.5, a temperature of 300 ^° C., a hydrogen molar ratio of 20, at a pressure of 100 kg / cm ² in the second stage reactor which was loaded with the same catalyst. The liquid substance produced was distilled and the fractions above 280 ^° C. were separated off; Then the measurements to determine the properties and the OK on heating oil tests were carried out. The results are shown in Table 3 and, as can be seen, excellent.

Example 4 ^{nis of}

S5 that with N

A tar-like substance produced by the cracking of catalyst

Ceria crude oil at 1300 ⁰ C during a contact time licri,

of 0.002 sec. was generated, was reduced under- Mesi

distilled tem pressure, and the fraction from 240 to Hei.t

400 ⁰ C, which has been deformed under normal pressure so shul

was was collected. The physical Eigen- ersij

10

were as follows: df viscosity = 6.5 Cp and HC

^{Were then in the} first stage, ^{organic metal based nanofinish} S ^s g ^s speed of 1.0,

T ⁴⁰⁰ ° ^{C and a} hydrogen of 10 at a pressure of 150 ke / cm ¹

^h ? ^{Ußreaktioöh} W ^^

it ^ohre W ^ * ^ ^cobal t-molybdenum, deposited

M ^{carrier (5: 5: 9} °) 'was ^loaded ; ^subsequent treatment at a

? ^dn i ^RESISTANCE ° ^{of '8'} * n 'tem- Wasserstoffmolvcrhält-

T? c'estil- ^28O ° ^C) ^ 'eseigi r uct as ^Prod wink removed up: - un the properties.! die, güh The results

' ^{riCi: e! lt} and, how from. ·! ser

Claims (7)

Patent claims: Je.doc, h bishe / fei "fuel are produced that meet all the requirements that such a propellant slide 1. A high performance fuel, characterized provided overall for supersonic aircraft are sufficient, as indicates that the high by hydrogenating, for example, heating values per weight and volume; iner from the WärmebehandJung a petroleum b unity, sufficient thermal stability and Geitummenden, tarry substance propellant formed - freezing point. substance has a specific gravity (17 from 0.86 to So is, for example, a process for hydrocracking l), 98 and a refractive index nf of 1.465 up to a petroleum fraction at which a proportion of an un- 1,500, a hydrogen content of more saturated components and an aromatic com- than 13% and one hydrogen-carbon atomic component are reduced as much as possible and has a ratio of more than 1.80, and as the proportion of a paraffin component is increased, Main component naphthenic or alkylnaph- a common one in today's petroleum refining industry thenischc hydrocarbons, without essential processes and consequently in economic Based on aromatic and aliphatic carbons - looks advantageous; in such a procedure Contains hydrogen. 15, however, by reducing the specific 2. Fuel according to claim 1, characterized in that the parafun component forming the cuphlhen ring reduces the calorific value per unit volume of hydrogen, as by a high-frequency drop, the thermal stability is poor and sorplion spectrum measurement is determined , more than insufficient, and the fuel obtained cannot be SO "/ ₀ , and that the aromatic ring 20 is considered to be sufficient at speeds with a Mach number of more than 2. As for the scite chains, none Contain hydrogen. Compensation for the low specific weight, 3. A fuel according to any one of claims 1 or 2, which is an adverse consequence of the above characterized in that it is a paraffinic component due to hydrogenation, one has on the other hand an aromatic oil in the presence of a cata- 25 envisaged a naphthenic component, lysators has been obtained by heat and many components, so-called oxotic combination treatment of a crude oil or a petroleum fraction have been synthesized. M. L e t ο r t at 700 to 230 ° C for a period of (Chim. et. Ind., March 1962), on the other hand, found 5 to 0.001 seconds. that a coal tar contains a large amount of an aromatic 4. Fuel according to claim 3, characterized in that it contains 30 components, and he has tried to distinguish that an aromatic oil with a boiling hydrogenation of this coal tar is a ^{fuel rich in naph range from 200 to 350 0} C and a specific thenischcr component to obtain. Weight from 1.0 to 1.3, a refractive index of. Although such a conception is in fact unique 1.55 to 1.68 and a hydrogen-carbon and exceptional, it must be taken into account that an atomic ratio of 0.5 until 1.0 has been hydrogenated. 35 coal tar a large amount of impurities, 5. Fuel according to claim 3, characterized in that the starting point is in the raw material hollow records that an aromatic oil has been hydrogenated contains such. B. a heteroaromatic which is a by-product or sump oil, the component with oxygen and / or nitrogen, so in the production of an olefin by thermal means that for this reason the hydrogenation reaction is not mixed Decomposition of a crude oil or a petroleum 40 is sufficient or insufficient, with the result that, fraction or one produced as a by-product, although the relevant teaching is already old, it is now residue oil is that is not practiced to a substantial extent in the gassing of an unearthed one. Crude oil or a petroleum fraction by high- As a result of years of research temperature decomposition occurred. of the void-like substances produced by the thermal 6. Fuel according to claim 3, characterized in that 45 high-temperature decomposition of a petroleum is produced, records that the aromatic oil before hydration was found to have such substances from a tion in the presence of a catalyst desulphurizes polycyclic aromatic component with very has been. there is little side celts that the impurities 7. Fuel according to claim 3, characterized in that petroleum has a tendency, as a result of the high drawing, that the aromatic oil for the period of 5 ° temperalurcrackens in the gas and pitch to coaguvon 1 min. To 5 hrs. Of further heating, and that therefore the hydrogenation process at treatment at 250 to 550 ° C is far easier to carry out than the above, is, if the boiling point, the specific gravity, based on the hydrogenation of coal tar the refractive index and the hydrogen-carbon process. The substance-atomic ratio of the aromatic oil is also a high-performance ^{fuel in the range from 200 to 300 0} C, I to 1.3, which is characterized in that the 1.55 to 1.68 or 0, 5 to 1.0. by hydrogenating one from the heat treatment of a petroleum-derived, tecr-like substance The invention relates to a high-performance propellant dete fuel a specific weight el '. ⁰ of 0.86 with high heating or caloric value per volume of from 60 to 0.98 and a refractive index "Γ of 1.465 to and unit weight, which has as a fuel for aircraft 1.500, ^e: NEN hydrogen content of more usable, the with supersonic speeds of 13% and one hydrogen-carbon atom. has a ratio of more than 1.80, and as it is already well known that such propellant main component naphlhenische or alkylnaphsioffe, such as. B. JP-4 (US standard), as they are conventional hydrocarbons used today without essential instructions for jet aircraft, partly in aromatic and aliphatic coals for so-called supersonic transport aircraft containing hydrogen.
Mach number greater than 2 are unsuitable. The fuel according to the invention has