FISHERIES RESEARCH BOARD OF CANADA

Translation Series No. 2624

Possibilities for utilizing macro and micro crystalline paraf fins

by R. Csikos, Gy.•Mozes, and S. Keszthelyi

Original title: Makro- es mikrokristalyos paraffinok felhasznaiasi lehetosegei

From:. .Magyar A'svanyolaj es Foldgazkiserieti•Intézet Kozlemenyèi (Reports of the Hungarian Mineral Oil andSatural Gas › ..

- Institute), 12 :. pp... 105-1_13, 1971 .

. .

. .

. .

Translated by the Translation Bureau(SG) •

Foreign Languages Division Department of the Secretary of State of Canada

• Department of the.Environment Fisheries Research Board •of Canada

Biological Station •, St. Andrews, N. B.

1973

17 pages typescript

4 .

r, eb* .

Jet3 DEPARTMENT OF THE SECRETARY OF STATE

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TRANSLATION BUREAU etetll e.`jetet'

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TRANSLATED FROM — TRADUCTION DE

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INTO EN

n g 1 ish

PAGE NUMBERS IN ORIGINAL NUMÉROS DES PAGES DANS

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PUBLISHER — ÉDITEUR

Hungarian Mineral Oil gt Nat. Gas Inst DATE OF PUBLICATION DATE DE PUBLICATION

106-113 ISSUE NO.

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Budapest, Hungary 12 1971

17

JUN 1 8 1073

UNTD Try.'

AUTHOR — AUTEUR

Csikos, R., Mozes, G. and Keszthelyi, S.

TITLE IN ENGLISH —• TITRE ANGLAIS

Possibilities for Utilizing Macro- and Iv:icro-crystalline Paraffins

TITLE IN FOREIGN LANGUAGE (TRANSLITERATE FOREIGN CHARACTERS) TITRE EN LANGUE ÉTRANGÉRE (TRANSCRIRE EN CARACTÈRES ROMAINS)

Makro- es Mikro-kristalyos Paraffinok Felhasznalasi Lehetosegei.

REFERENCE IN FOREIGN LANGUAGE (NAME OF BOOK OR PUBLICATION) IN FULL. TRANSLITERATE FOREIGN CHARACTERS.

RÉFÉRENCE EN LANGUE ÉTRANGÉRE (NOM DU LIVRE OU PUBLICATION), AU COMPLET, TRANSCRIRE EN CARACTÈRES ROMAINS.

Reports of the Hungarian Mineral Oil and Natural Gas Institute,

Magyar Asvanyolaj es Foldgazkiserleti Intezet Kozlemenyei

REFERENCE IN .ENGLISH — RÉFÉRENCE EN ANGLAIS

see above

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Possibilities For Utilizing Diacro-and

Nic roc rys tal l ine Paraf f ins .

Dr. R. Csikos, Dr. G. Mozes °_ S. KeszthelyiReports of the Hungarian Mineral Oil & Natural Gas

Inst., Vol. 12, 106-113, 1971.

During the last decades, in Iiungary, petroleum production

increased threefold t.rith renewed interest in the production of paraffin

oils.

This has , naturally, brought about a s ignif i.cant increase in

the quantity of available paraffin and petrolatum byproducts.

The domestic petroleum industry has, up to now, produced only

macro-crystalline paraffins having a melting point of 50-580C.

Petrolatums containing micro-crystalline paraffins were utilized as

fuel oils. The expansions effected during the last few years will allow

the production of macro-crystalline as well as micro-crystalline paraffins

of different properties.

In view of the above, our Insjitute has, for the post few years,

investigated the production technic;ues, classification and processing of

macro- and micro-crystalline paraffins as well as the uti.li7ation of the

byproducts. This report gives a short outline of our research and results.

U:vI. •., . ( r`

SOS-200-10-31

DEPARTMENT OF THE SECRETARY OF STATE

TRANSLATION BUREAU

1 • ^ ^ • . .

'nllli(^i[l^^4,

7630-21-02G.0332

•L.

We hava attempted to resolve local problems which have arisen

as a result of the new erpanded facilities rather than develop new

technological processes.

Fractionation of Micro-crystalline Paraffins.

In order to enlarge the selection of micro-crystalline

paraffins, we hava investigated the solvent fractionation of

petrolatums, i.e residual oils.

Two-Step Fractional Crystallization of Residual-Oil Petrolatum in the Laboratory.

Table 10-1.

Experimental Conditions First Step Second Step

Temperature, °C. +30 0 Solvent Composition

MEK, tf. % 70 70 Benzol, tf. % 30 30

-pantity of Diluting Solvent, se 700 1440 Quantity of Washing Solvent, s.% 400 370

Hard, micro- Soft, micro- Properties crystalline crystalline

paraffin paraffin

-

Yield, s.% 24,8 29,3 Density 0.7991/80°C. 0.8138/70 00 Viscosity, cSt/10000. 10,25 10,33 Melting Point, 0C. 75 53 Penetration 100 g/25 0C., 0.1 mm.(tu) 17 39 Oil Content, s. % (ASTM) 6,70 3,0 Y

Breaking Point (Fracs), °C. over +20 under -20 lso/normal hydrocarbon ratio s 0,3 . 2,8 Tensile Strength on 00C., kp/cm2 27 17 Molecular Weight 561 591

.'"

3

It can be seed from the results of our experiments that by using

residual-oil petrolatum or residual-oil, multi-step fractional distilla-

107 tion will yield hard, rigid, micro-crystalline paraffins of high melting

points as well as soft micro-crystalline paraffins showing plasticity .

even at low temperatures (1, 2). Table 10-1 shows results obtained by

the two-step fractional crystallization of residual-oil petrolatum having

an oil content of 24.0% and a pour temperature of 67°C. Temperature: for

the first step was +300C. and + 0°C. for the second step. Diluting and

washing solvents consisted in both cases of 70% methylethyl ketone and

30% benzol. During the first step we obtained a rigid and hard micro-

crystalline paraffin having a M.P. of 75°C. and a high breaking point

while during the second step, a soft, tough micro-crystalline paraffin

formed having a M.P. of 53°C. with a low breaking point and high iso-

carbon content. Therefore, using fractional distillation, products of

different composition and properties can be obtained. Using these as

additives, paraffin-base preparations of special characteristics result.

E.g. By the gradual addition of the soft, tough product obtained in

Step 2 having a -20°C. Fraas-breaking point and high hydrocarbon content,

coating paraffin preparations showing elasticity even at low temperatures

can be obtained.

Table 10-2.

Significant Properties of COmpounded and Additive Paraffins.

M.P. Oil Viscosity Fraas- Specific Ductility Tensile Penetration °C. Content at 1400C. breaking Gravity at +35°C. Strength at 35°C.

s.% cSt point °C. at 0°C. mm. at 0°C. 100 g/5s kpcm/cm2 (pulling (ASTM needle)

vel. = 0.1 mm. 50 mm/p)

. kp/cm2 .

ove.r Plate paraffin 53 . 0.75 1.85 +20 0.53 7.7

Compounded plate paraffin 60 4.3 3.22 -8 1.1 148 20.7 102

, Compounded paraffin containing polyethylene • wax, viscosity 6 se 1029 cSt/140°C. 83 4.04 5.2 +13 2.3 86 22.15. 88

•

Compounded paraffin containing ethylene- - vinylacetate copolymer M. index 6 s.% 22-28 68 under g/10p 4.04 12.5 -20 3.4 39 24.6 82

Compounded paraffin containing ethylene- vinylacetate copolymer, . K. index 6 se 125-175 69 under g/109 4.04 11.92 +19 3.4 5 24.2 63

5

Preparation of Special Paraffin Products by Compoundirg and Additives.

In addition to the production of micro-crystalline paraffins by

fractional crystallization, we have also studied the possibilities of

producing normal plate paraffin by compounding and additives (3).

Residual-oil petrolatum of 6-10% oil content was used. The rate of

compounding was selected by using compounded paraffin of a lower than

5% oil content. By varying the ratio of plate paraffin and residual-oil

paraffin, i.e. the type and concentration of the additive, paraffin-base

108 preparations of different properties were obtained. The more important

properties of some of these preparations are shown in Table 10-2. We

have added polyethylene waxes and ethylenevinylacetate to the compounded

and additive paraffins (4). It is apparent that the properties of plate

paraffin are changed considerably by compounding and the use of additives.

By compounding paraffin and residual-oil petrolatum, we obtained a product

having better tensile strength, plasticity, but lacking sufficient tough-

ness. Using polyethylene waxes of the sanie concentration, we obtained

preparations having a higher melting point and lower viscosity than with

the use of ethylenevinylacctate copolymers. It is also apparent that

among the copolymers, additives having a lower melting point and higher

vinylacetate content give products which have a lower breaking point and

are tough. Likewise, copolymers having a lower vinylacetate content and

higher melting index, give preparations which are also tough but have low

ductility and higher breaking points.

6

Oxidation of Micro-crystalline Paraffins.

It is established that oxidation of paraffins gives synthetic

fatty acids; hydrogenation of their esters produce fatty alcohols of

various carbon atom numbers; oxidation in the presence of.tartaric acid

directly afford secondary fatty alcohols (5, 6). Furthermore, efforts

have been made to produce partially-oxidized micro-crystalline paraff ins

which would replace natural waxes. Since this method of producing

synthetic fatty acids and fatty alcohols is not considered economical,

our Institute has primarily concerned itself with the production of

oxidized micro-crystalline paraff ins and based on these, the production

of synthetic waxes.

The raw material used in our sttzdies consisted of residual-oil

petrolatum of medium oil content obtained from domestic petroleum. By

using solvent oil extraction, we obtained micro-crystalline paraff ins of

low oil content. The oil extraction was achieved by the use of 30% acetone,

35v benzol and 357, toluol at +20°C. and +0°C. Table 10-3 shows the

significant characteristics of the basic substance and the micro-crystalline

paraf f in.

7

Table 10-3.

Characteris tics of Residual-Oil Petrolatum and Solvent Oil-Extracted Crystalline Paraffins.

Local residual Microcrystalline Microcrystalline • oil petrolatum paraffin obtained paraffin obtained

at +20°C. at +000. —

Pour Point, °C. 72 78 75 Viscosity, cSt/100°C. 12.19 . 9.86 11.18 Oil content, s.% 10.3 3.1 5.0 Penetration (25 C., ASTM) 0.1 mm. 95 15 27

Sulfur content, s.% 0.15 Molecular 14;›,ht 617

The partially-oxidized micro-crystalline paraffins were obtained

by the autoxidation of micro-crystalline paraffins as shown in the previous

table, having a low oil concentration of 3.0% and 5% respectively. The

autoxidation was accomplished at 120° C. and 120 1/kg. specific air pressure

per hour. Cobalt stearate was used as the catalyst at a concentration of

0.14%. Duration of the oxidation experiments varied from 7 to 22 hours

depending on the acid concentration of the products. Table 10-4 shows a

summary of significant properties of partially-oxidized products obtained

• from micro-crystalline paraffins having various pour points. At higher

109 pour points, i.e. higher saponification, a significant increase in

viscosity and penetration occurs. Oxidized products obtained from micro-

crystalline paraffin of higher pour point and lower oil content and having

similar acid strengths, i.e. saponification number, had significantly lower

viscosity and penetration. From this example it can also be shown that by

109

8

chaeng oil extraction conditions and the degree of oxidization, as well

as by mixing products of different properties, end-products showing

markedly varying characteristics result.

Table 10-4.

Significant Properties of Oxidized Micro-crystalline Paraffins.

- Oxidation products Oxidation products obtained from micro- obtained from micro- crystalline paraffins crystalline paraffins

at 0°C. at +20°C.

Acid strength, mgKOH/g 27.0 63.0 65.0 Saponification No. mgKOH/g 53.0 126.0 128.0 Pour point, °C. 69.0 64.0 68 Viscosity, cSt/100 0C. 17.6 49.2 28.8 . Penetration (25°C. ASTM needle)0.1 mm 54 113 56 Ester conc. mgKOH/g 26 63 63 Ester/acid ratio 0:96 1.0 0.97

• Fatty acid esters of higher alcohols, e.g. diglycol stearate,

belong to the so-called emulsion wax groups. These synthetic waxes are

used in the manufacture of many household chemicals. Our Institute

considered the possibility of obtaining products of different properties

by esterification of free fatty acid and fatty acid ester-containing

partially-oxidized micro-crystalline paraffins with higher alcohols.

During our experiments, we used various glycols as esterizing agents

after catalytic reduction of partially-oxidized micro-crystalline

paraffins without separation of non-saponifiable portions.

9

Esterification was accomplished with ethyeleneglyeol, diethyleneglycol

and propyleneglycol. p-toluol sulfonyl acid was the catalyst. Experi-

ments conducted so far cover mainly the properties of products containing

glycol esters as compared to properties obtained with partially-oxidized

products.

Table 10-5 shows the significant properties of oxidized micro-

crystalline paraffin of 65 mgKOH/g acid concentration esterified with

propyleneglycol in relation to the aci.d-dlcohol molecular ratio.

Esterification was done at 104-1180C.; duration of esterification was no

longer than one hour.

Micro-crystalline paraff ins containing propyleneglycol esters

are plastic products. Generally, it was determined that products contai-

ning glycol esters prepared f rom residual-oil petrolatum by oil extraction,

autoxidation and esterification of the partially-oxidized micro-crystalline

paraffin, had a pour point of 66-680C., a viscosity of 23-38 cSt. at

1000C., and penetration'of 50-90, 0.1 mm. as measured on the ASTM standard

needle at 250C. The acid concentration of the end-products was 9-27 mgKOH/g

depending on the original acid-alcohol molecular ratio.

We are presently investigating the technical application of micro-

crystalline paraffins containing glycol esters. Depending on these results,

we will be able to determine their usefulness. Should the results be

favorable, production of synthetic waxes during the production of petroleum

10

as by-products, i.e. preparation of micro-crystalline paraffins, might

110 become economically feasible.

Preparation of Chlorparaffins.

It is well known that chlorinated paraffins are used in the

plastics, paid:and varnish, petroleum, textile, paper and rubber

industries. It is expected that domestic demand for PVC will be on

the increase (5).

Table 10-5.

Propyleneglycol Esterification of Oxidized End-Products • of Micro-crystalline Paraffins having a Pour Point of 78°C.

Acid/Alcohol Molecular Ratio Product Characteristics 1:0.5 1:1 1:2

Acid conc. of esterification product, mgKOH/g 26.16 17.62 9.01

Saponification number, mgKOH/g 125.40 120.38 112.78 Ester concentration, me03/g 99.24 102.76 103.76 Viscosity, cSt/100 °C. . 29.2 27.2 20.9 Rotational congealing Point, °C. 67 67 67 Penetration (25oC., ASTM needle,

100 g/5s), 0.1 mm. 60 68 88 Fraas Breaking Point, 0C. under -15 -20 under -25

Chlorinated paraffins are used as cheap, secondary softeners

in the manufacture of PVC. Having an identical chlorine content, solid,

pure n-paraffins afford products of lower viscosity, greater stability

and better color than products obtained from plate paraffins. Due to

domestic conditions, we have primarily concerned ourselves with the

chlorination of plate paraffins.

11

In accordance with data in the literature, we have found that

the chlorine content, color and stability are deciding qualitative

factors in the utilization of chlorinated paraffins whereas specific

gravity and viscosity depend mainly on the properties of the basic

substance. Viscosity formation of the products is an example. These

properties can be greatly influenced by the variation of molecular

weight and built-in chlorine content of the original material. This

is shown in Figure 10-1 where the viscosity measured at 50 0 0. is

plotted against the abovementioned parameters.

Our experiments enabled us to establish a process for the

chlorination of domestic plate paraffin having 20-27 carbon atoms,

the final product having a 40-50% chlorine content which meets

international standards. Variation from these standards is only

shown in viscosity and specfic gravity. Basic chlorinated paraffins

used in the softening of PVC production consist of a mixture of hydro-

carbons containing 16-20 carbon atoms. In order to determine the

feasibility of using our product in PVC production, despite deviation

in viscosity and specific gravity from established standards, further

experiments were conducted.

In addition to producing 40-50% chlorparaffins, our Ineitute

bas also prepared a 70% product.

I350^

Molecularwe ight

340^0 F40

133^ ^-Y

30

320-

f

ZO

3•10-)

, 3004-^---T, -- - ,-r -

_^-- r- 00 100 2GZ) 300 400 500 600 700 B00 900 7000 1f00

Viscosity at 500C., cSt.

Figure 10-1. Relationship Between Mol. Wt.,Chlorine Content and Viscosity.

12

Chlorine

content

S.7-

Our Institute has also investigated the reactor technology of

reagents used in chlorination. We have so far examined the optimum

development of tubular reactors, conditions for the formation of

isothermal reactors and the f eas ib il ity of chl or inat ion in the s pec ial ,

self-circulating reactor developed by the Institute.

Pyrolys is of Paraf f ins for the Production of alpha-olef ins .

Since the 1940's, interest has grown in the manufacture and use

of alpha-olefins. In addition to established methods for the preparation

of high hydrocarbon alpha-olefins, the thermal heat combustion of paraffins

and paraffin-containing substances should also be investigated.

Published reports on the thermal combustion of paraffins and

paraff in-containing substances cover experiments conducted with paraffins,

n-hydrocarbons and circulatory residual oil products formed during catalytic

cracking. The principal aim in such production of alpha-olefins is the

utilization of byproducts, although the reaction mechanisms and reactor

technology are not, as yet, fully developed.

Our Institute has investigated the heat combustion of petrolatutns.

The following are some of our experiments and results.

13

Duriag our experiments, we have studied, among others, the

heat *combustion of petrolatum having a Molecular weight of 470,

40% oil content, 520-600DC, furnace temperature and 1-2 hour decompo-

sition time under 40% vapor pressure. This petrolatum consisted

mainly of paraffins having more than 34 carbon atoms and alkyl

aromatics of high Molecular weight. The yield contained only 10%

paraffin having a 20-34 carbon atom number. Figure 10-2 shows the

total condensation obtained as a result of pyrolysis aid the yields

of hot, liquified olefin fractions up to 3200C. in relation to furnace

temperatures. It is apparent that the condensate yield within the

temperatures used decreases with elevation in temperature while the

amount of the hot fractions up to 3200C. increases. We have determined

that at higher furnace temperatures, the percentage increase in the

quantity of initial petrolatum present in the unsaturated hydrocarbon

fraction of the gas was higher than that of the saturated hydrocarbon

fraction. The ethylene content of the gas reached its maximum value

at 540-560°C. furnace temperature. Examination of the dis tillates

indicated the following main characteristics: olefin content is at

maximum at 530-560°C. furnace temperature; during the same conditions,

with higher boiling temperatures of the fractions, the alpha-olefin

content decreases from 65% to 40%, and the total olefin content from

81% to 54%. 80% of the olefins consisted of alpha-olefin, 20% vinylidene

and chain-linked structured olegin.

14

Figure 10-2.

Petrolatumyield, s .%

o Q--

530 540 550 560 570 580 590 600

Furnace-emanating temp.oo.

112

Product yields in relation .to emanating temperatures.(a) total condensate(b) hot, 1 iquef ied olef in fraction up to 3200C.

Table 10-6.

Two-Step Cracking_of Petroleum.

Cracking Characteristics Cracking Cracki.ng Balanced Total

Furnace temperature, OC. 600 600 600mount of water added, s.% 40.52 38.23

Fraction yield., s.%initial B.P. 900C. 10.17 5.04 12.50

90-170oC. 5.90 5.17 8.09170-2700C. 8.71 6.31 11.46270-3200C. 3.45 4.57 5.32

Total up to 3200C., ^ 28.23 21.10 37.37Residue over 3200C., % 40.07 55.64 20.85Distillation loss, %, 1.18 2.79 2.28

Total condensate, %, 69.48 79.53 60.50Gas yield, ô 28.03 15.72 35.14Condensate obtained on carbon, 2.48 4.74 4.36

Total 99.99 100.00 100.00

113

15

Table 10-7.

Gas Analysis of Two-Step PetrolatUm Pyrolysis.

Analytical Data 1st step 2nd step Balanced total

Gas density, g/1 1.2226 1.2170 - Gas yield, % 26.51 14.40 31.84 Gas composition, s.%

112 0.35 0.43 0.37 CH4 11.17 12.45 11.38

C2H6 8.54 8.43 8.52 C3H8 2.37 • 2.07 2.31

C41110 1.38 1.13 1.34

CnH2n4-2 23.64 24.05 23.55 C2114 28.56 30.53 28.90 C3116 22.09 22.88 22.22 C4H8 18.31 12.75 17.87

CnH2n 68.97 69.13 68.99 W16 7.23 6.39 7.08

Total 100.01 100.00 99.99

we have also conducted two-step pyrolysis experiments with the

same petrolatum. These were done at 600 °C., lasted 1.5s. in the presence

of 40% vapor pressure. Table 10-6 shows balanced totals and Table 10-7

the composition of the gas. Data in Table 10-6 shows that during the

second step, the gas yield as well as the amount of hydrocarbon at 3200C.

hot olefin decreased. Data in Table 10-7 demonstrates that the olefin,

i.e. alpha-olefin content of the reaction products does not vary giei-

ficantly between steps. According to our experiments, at two-step

pyrolysis, the processed petrolatum gives 42% hydrocarbon fraction at

320°C. and cracked gasof 35% olefin content.

- • ,

16

In our short report, we could only give a partial summary of

our experiments with paraffins. We could not cover, in detail, questions

relating to the analytical, structural and piactical aspects of paraffins.

Summary.

In the processing of paraffin oils the problems of processing or

utilizing paraffin by-products are necessarily raised.

In addition to producing normal quality plate paraffins micro-

crystalline paraffins with different properties may be produced by carrying

out crystallization in several steps. In this way the assortment of products

may be enlarged and, their field of application extended. The application

of macro- and micro-crystalline paraffins may be extended further by using

these products as additives. The products made in this way can Meet the

most varied demands.

Possibilities for using paraffin and paraffin by-products in

chemistry exist mainly in the fields of paraffin oxidation, paraffin

pyrolysis and chlorinated,paraffin production.

Our Institute has studied questions relating to the utilization

of paraffins for several years. In the present paper an account is given

of the research work conducted up to now and of its results.

Literature.

1. Teubel, J, Schneider, W. and Schmiedel, R.: Petroleumparaffins, Leipzig (1965).

2. Freund, M., Keszthelyi, S., Csikos, R. and Mozes, G.: Che. Techn. 19, 688 (1967).

3. Keszthelyi, S., Szirbek, J. and Fenyi, M.: International Symposium "Paraffins and Waxes", Weimar (1969).

• 4. -: Packaging, No. 62, Sept. (1962).

5. Asinger, F.: Paraffins, Chemistry and Technology, Pergamon Press, Oxford (1968).

6. Brunstejn, B.A., Klimenko, V.L.: Himicseszkaja Promuslennosztj No. 9, 22 (1963).

17

Submitted: September 28, 1970.