DE1234346B - Process for the production of a petroleum-hydrocarbon mixture - Google Patents

Description

GERMAN WfflTWl PATENT OFFICE Deutsche KL: 23 b -1/04

EDITORIAL

Number: 1234 346

File number: E 23668IV d / 23 b

^ 234,346 Filing date: October 11, 1962

Opened on: February 16, 1967

The invention relates to a process for the preparation of a petroleum hydrocarbon mixture containing 4 to 5 percent by weight of monomeric and dimeric cyclodienes, of which at least 1.5 percent by weight are monomeric cyclodienes, and for polymerizing to petroleum resins with a color between 12 and 13 Gardner units and a softening point between 95 and 105 ^c C, which is characterized in that a steam-cracked hydrocarbon mixture containing 4 to 5 percent by weight of monomeric and dimeric cyclodienes but less than 1.5 percent by weight of monomeric cyclodienes is first analyzed for its gelialt of monomeric and dimeric cyclodienes and then subjected to a dimerization treatment, the temperature and duration of which are determined by calculation as a function of the analytically determined composition of the steam-cracked hydrocarbon mixture.

It is known that the color, softening point and yield of a resin obtained by polymerization obtained from steam cracked petroleum hydrocarbon mixtures containing monomeric and dimeric cyclodienes if the respective percentages of the constituents are known are. By adjusting these components accordingly, you can create a resin with a color between 12 and 13 Gardner units (according to ASTM D 154-50, measured using a solution of 50 percent by weight resin in toluene) and a softening point of 95 to 105 ° C.

Since the proportion of cyclodienes in the hydrocarbons to be used depends on the method of operation the steam cracking plant can be different, the percentage of cyclodiene must be before the polymerization of the mixture can be regulated by adding monomers and dimers.

A hydrocarbon mixture that polymerizes to form petroleum resins with a color between 12 and 13 Gardner units with a softening point between 95 and 105 ° C is suitable be steam-cracked light petroleum hydrocarbon mixture (boiling range 35 to 190 ° C), the 4 to 5 percent by weight cyclodienes, based on the Koh-Ienwasserstoffgemiseh ^ contains, of which at least 1.5 percent by weight are cyclodienes.

If up to now the petroleum hydrocarbon mixture did not contain the desired ratio of monomeric to dimeric cyclodienes, the cyclodienes would first have to be divided into a first fraction with a boiling point below 120 ° C, which contained the monomeric cyclodienes, and a second fraction with a process for the preparation of one
Petroleum hydrocarbon mixture

Applicant:

Esso Standard Societe Anonyme Francaise, Paris Representative:

Dr. W. Beil, A. Hoeppener and Dr. HJ Wolff,
Lawyers,

Frankfurt / M.-Höchst, Adelonstr. 58

Named as inventor:
Pierre Delbende,

Gruchet-Ie Valasse _j Seine-Maritime;
Pierre Bernard, Le Havre, Seine-Maritime;
Marcel Prillieux,

Mont-Saint-Aignan, Seine-Maritime (France)

Claimed priority:

France of October 12, 1961 (875 813)

a boiling point above 120 ° C, which contained the dimeric cyclodienes, are fractionated. Then in simple cases it was possible to add part of the second to the first fraction.

In accordance with the invention, this desired ratio is found in a steam cracked petroleum hydrocarbon mixture directly achieved by the monomer-dimer equilibrium of the cyclodienes regulated at atmospheric or reduced pressure and suitable temperature.

If by analyzes quantitatively the cyclodienes contained in the petroleum hydrocarbon mixture are (especially monocyclopentadiene and its dimer and monomethylcyclopentadiene and its Dimers), can be determined taking into account the results determined by these analyzes Determine the percentages of temperature and duration of treatment that the hydrocarbon mixture is in must be subjected to a container under pressure in order to achieve the desired monomer-dimer ratio to achieve.

To carry out the method according to the invention, a device is used which has a Analysis station and a computing station contains. The results of the Analysis passed to the computing station, in which the

709 509/401

residence time and the temperature for the treatment of the hydrocarbon mixture is determined.

The resulting hydrocarbon mixture with the desired ratio between monomeric and dimeric cyclodienes can then be polymerized either batchwise or continuously in the customary manner will.

The required total content of monomeric and dimeric cyclodienes in the starting material can be according to any known method, e.g. B. by distillation, can be adjusted when the cyclodienes are enriched or need to be reduced.

In an example which serves to illustrate the invention, a steam-cracked petroleum hydrocarbon mixture is used with a density of 0.750 with the following analysis based on the weight of the Hydrocarbon mixture, used as raw material:

Monocyclopentadiene (CPD) 0.88%

Monomethylcyclopentadiene (MeCPD) .. 0.21%

Dicyclopentadiene (DCPD) 1.76%

Dimethylcyclopentadiene (DMeCPD) ... 1.71%

4.56%

25 and a is the initial concentration of the monomer (t- 0) and χ denotes the concentration at time t of the monomer transformed into the dimer.

However, at a high temperature, the dissociation reaction of the dimer prevails opposite to the above process. This dissociation reaction is a first order reaction. Your constant k ₂ is therefore

~ = k ₂ (by)
German

at a certain temperature, where t is the time, b is the initial concentration of the dimer (t- 0) and y is the concentration of the dimer transformed to the monomer at time t.

In general, the dimerization and dissociation reactions take place at a certain temperature simultaneously. The change in the overall conversion, if one starts from the monomer, can can be expressed as follows:

= Ar ₁ (a - xf ¹ - k ₂ -
German 2

This feedstock is said to be converted into a hydrocarbon mixture that is 4 to 5 percent by weight contains monomeric and dimeric cyclodienes, of which at least 1.5 percent by weight is monomeric Are cyclodienes.

According to the above analysis, the first requirement is met (4.56% cyclodienes are in this Raw oil available); on the other hand, the second requirement is not met, since only 1.09% monomers are present.

This crude oil must therefore be treated so that a new equilibrium between monomers and dimers, this treatment being referred to below as "equilibrium treatment" will. The results of this treatment are that some of the dimeric cyclodienes become monomeric Cyclodienes is converted.

For this purpose, the optimal conditions for the "equilibrium treatment" must be known be, d. H.

a) the temperature at which the treatment is to take place, and

b) the treatment time so that at least 1.5% monomers are obtained in the crude oil.

50

The main factor is the time during which a steam-cracked crude oil is at a certain temperature must remain in order to achieve a given monomer-dimer ratio.

It is widely known that mono- (cyclopentadiene) (CPD) does not matter whether it is in the form of a pure Liquid, gas or in various solvents, at ordinary temperature to di- (cyclopentadiene) (DCPD) dimerized]. Similarly, mono- (methylcyclopentadiene) dimerizes to Di (methylcyclopentadiene).

This dimerization reaction is a second order reaction. It is characterized by a constant

German

at a certain temperature, where t is the time at a certain temperature, where t is the time, a is the initial total concentration of the monomers transformed into the dimers at time t _{, Ar 1 is} the dimerization constant at the prevailing temperature and k _{2 is} the dissociation constant at the prevailing temperature is; if you start from the dimer, you can write in the same way

dv
German

where t is the time, b is the initial total concentration of cyclodiene in the form of dimers, y is the concentration of the dimer converted to monomers at time t and k _x and k _{2 have} the meanings given above.

In the state of equilibrium at the temperature in question, it is possible for the ratios To write (1) and (2),

dx German

dv
German

Ar ₁ (a - x) ² - Ar ₁ - = O
2

= k ₂ {by) -k _x (2y ) ² ^ o,

whose roots are X ₁ and X ₂ and J ₁ and y ₂ , respectively.

If one also calculates the concentration in moles per liter of the monomeric cyclodienes with M and the concentration in moles per liter of the dimeric cyclodienes with D in the present state of equilibrium, the equilibrium equation is obtained

M ² D

& 2

T ₁

at the temperature in question.

The rate constants Ar ₁ and k ₂ for different temperatures can be calculated according to Arrhenius:

_ ^E.

k = Ae ^RT

where k is the constant variable, A is the experience constant, E is the experimental activation

5 6

energy, T is the absolute temperature at which the CPD: 0.88 percent by weight, viz

Reaction takes place and R is the ideal gas constant q gg. • ^ qqq. q y ^ o

mean. - = 0.1 mol / 1.

In the case of 100 · 66, which serves to explain the invention

Example was found: 5 _{MeCPD: 0.21} percent by weight, namely

ino- ir * 1 ^{16 400} 0.21 · 1000 · 0.750 _n ^ _liir

¹ Ogi ₀ K ₁ = °, 1 - = 0.02 mol / 1.

4.57 100-80

whereby

Ar ₁ in (MolZl ) ^-1 Sec "" ¹ io DCPD: 1.76 percent by weight, namely

1.76-1000-0.750 _ .... ...

is expressed, and - ^O > ^L M-oi / i.

ι, _ "n ³⁴⁵⁰⁰

IOgi ₀ K ₂ - ΐό, ν- _457T , DMeCPD: 1.71 percent by weight, namely

from which '* 1.71-1000-0.750 ₌

L 18100 100-160

logio = 6.9

Zfc ₁ 4.57 Γ

1. Determination of the treatment temperatures

results. 20th

By graphical representation by adding on the m the number of moles per liter CPD and η the

1 j fj ^ j-ii u -mj number of moles per liter of MeCPD ₅ that according to the loading

Abscissa ~ = r and on the ordinate log ~, and, ", ^,"'." _R.

T ^ö Ar ₁ ^ö action is to be obtained. These values of w

Ar ₂ , ... "" ti. τ. 11 1 j and η should agree with the following condition-

if one knows V ^l , it is possible to quickly find - = ■ and .. ^ö <= 0

Κ ⁰ T 25 votes:

so to determine Γ.

The result can of course also be calculated. m-bb- IOU ₊ nW * 100 ₌ ^

The treatment time at the candidate 100 x 0.750 100 x 0.750

Temperature is determined as follows: 4 t.- -4

The expressions (1) and (2) (above) for the speed ^{are used}

The overall reaction times can be calculated in the following 11.25 - 66 m

Form: ⁿ = ~ ( ⁴ )

öU

dx

^{1K 1 / y 2} ^ _'35 It was stated above (3) that

M ² k.

if monomeric cyclodienes are assumed,
or D Ar ₁

dv.,,. ,. is

- 4 Ic ₁ (y - JA ₁ ) (j - J ₂ ), j _n considering the fact that cyclopentadienes

"* and methylcyclopentadienes are present, both in

when starting from dimeric cyclodienes. Working in their own mind becomes a balance

By integrating this differential equation, it is obtained at

possible, χ or y as a function of the residence time _a

at the temperature in question, ₄₅ ^{m r} L

press 0.3 - m _ k _z _ 0.18 - η

lx - x 2 Ar ₁ 2

-log = t + constant,

ki {X ₁ X ₂ ) χ X ₂ or

VOJ

will, and

50 2 m ² _ 2n ² _ K_

when starting from monomeric cyclodienes 0 3 - m ~~ 018 "~ k

^lo S ^ r ^ r = ^t + constant, _. _, .. ₊ k,

From equations (4) and (5) it is possible to

4 Ki (ji - J ₂ ) y ~ '55 ^{m uncl n una} - thus -γ- to be determined.

According to the calculations made, if necessary, under

when starting from dimeric cyclodienes. Use of curves are made,

The computing station, which is seen in the industrial plant, makes it possible to carry out these calculations

carry out and the required temperature and 60 m - 0.09 mol / 1,

To determine treatment time. and η - 0.066 mol / 1,

A simple example for a crude oil with the _k characteristics given above enables the and -ξ- = 0.077 mol / 1,

Establishing the results of these calculations. ¹

The respective molecular weights of CPD, DCPD 6s thereby obtained and DMeCPD be 66, 132, 80 and 160 g, and _k has the crude petroleum before treatment the following Iogi ₀ - ^5. - = -1.114.

Composition (based on the total weight): K ₁

Claims (2)

By means of the graphic representation or the k. In the calculation given above, Iog ₁₀ -γ- is obtained as a function of the reciprocal value of the absolute temperature, ie y = 0.00203, namely r = 493 ° C, ie 220 ° C. 2. Determine the treatment time t at 220 ° C a) The system consists of MeCPD - DMeCPD It was explained above that the time is determined by the following ratio: ■ 1 log— —- = t + constant 4Ai 0Ί -J ₂ ) (the sign must be positive) results from the fact that
with Λ = J ₂ Syfc ₁ 8 A ₁ 8 A ₁ bk ₂ 4 A ₁ 8 A ₁ 16,400 6 A ₂ 4 A ₁ Iog ₁₀ A ₁ = 6.1 ΐΐ2Ι ^ = -1.17 4.57 (273 + 220) this _{gives A 1} = 6 · 6 · IO- ² (Mol / 1) ^-1 sec ~ Furthermore, it is determined by calculation: A2 A ₁ and b = 0.09
therefore y _x = 0.033
and J ₂ = 0.052 At the time / = 0, j = 0.01
the constant 44.2. When y - 0.032 mol / 1, the equilibrium state (j = 0.033 mol / 1) is practically reached. The time t (the seconds required to achieve y = 0.032 mol / 1) is determined (after calculation) as follows: r = 153 seconds, ie 2 minutes and 33 seconds. It is therefore possible to determine that after 3 minutes at 220 ^c C the petroleum contains: = 0.077 ΙΟ ^-3 moles / cc IO ^-3 mol / ccm ΙΟ- ³ mol / ccm IO ^-3 mol / ccm. IO ^-3 mol / ccm, therefore 0.033 x 160 x 100 = 0.71% MeCPD 100 x 0.750 (1.71 + 0.21) - 0.71 = 1.21% DMeCPD b) System of CPD and DCPD In this system, the time it takes to reach equilibrium plays a role, since a very small part of the monomers is dimerized. No matter how long the period is, it will definitely find ξ _0: 0.88% (f = 0) 0.09 x 66 x 100
100 x 0.750 = 0.79% CPD (equilibrium), _6s therefore the sum (MeCPD + CPD) is always greater than 1.5% after three minutes of treatment at 220 ° C. If you want to determine the percentage of CPD that remains after 153 seconds of treatment at 220 ° C, it is enough to apply the following equation: Iogx = t + constant, X Xh A ₁ (X ₁ X ₂ ) and when the calculations are complete, it is found 0.206 moles / 1,
0.094 moles / 1, χ -χ 0.094-66-100. ,. . _rnn a - χ = = 0.827 weight percent CPD. 1000 x 0.750 15 Conclusion Contains raw oil 0.88% CPD,
0.21% MeCPD,
1.76% DCPD,
1.71% DMeCPD; 25th 30th 50 55 after 153 seconds at 220 ° C contains the crude oil 0.83% CPD,
0.71% MeCPD,
1.81% DCPD,
1.21% DMeCPD. The above example shows that it is possible in this way to determine the composition of a crude oil with regard to the monomer-dimer ratio that is to be obtained, directly thereby to modify that one regulates the temperature and the reaction time to an equilibrium to obtain. The computer provides the required data and monitors the conditions of the individual levels (Valves, heating, etc.) in which the crude oil must remain before it is introduced into the polymerisation stage will. Patent claims: 1. A process for the preparation of a petroleum hydrocarbon mixture that is 4 to 5 percent by weight contains monomeric and dimeric cyclodienes, of which at least 1.5 percent by weight is monomeric cyclodienes and that for polymerization into petroleum resins with a color between 12 and 13 Gardner units and a softening point between 95 and 105 ° C, characterized in that a steam cracked Hydrocarbon mixture containing 4 to 5 percent by weight of monomeric and dimeric cyclodienes, however contains less than 1.5 percent by weight of monomeric cyclodienes, initially based on its monomeric content and dimeric cyclodienes and then subjected to a dimerization treatment whose temperature and duration depend on the analytically determined composition of the steam-cracked hydrocarbon mixture can be determined by calculation. 2. The method according to claim 1, characterized in that a hydrocarbon mixture is used Steam-cracked petroleum hydrocarbon mixture is used, the monomeric and dimeric cyclopentadienes and contains methylcyclopentadiene. Considered publications:
French Patent No. 1,251,311. 709 509/401 2.67 © Bundesdruckerei Berlin