The method of determining the group of the hydrocarbon composition of the heavy distillate fractions

 

(57) Abstract:

The invention relates to methods of analysis of products of processing of oil on the group hydrocarbon composition and determination of potential content refined, dewaxed oils, heavy distillate fractions, and also to identify potential content in the raffinate dewaxed oil by calculation. The method of determining the group of the hydrocarbon composition of the heavy distillate fractions is carried out by desorption separate hydrocarbon groups of dewaxed residue distillate or raffinate consistently solvents: petroleum ether with limits of boiling temperatures of 40-70C., a mixture of petroleum ether and toluene, taken in the ratio of 95:5 to 75:25 vol.% toluene, alcohol-toluene mixture, taken in the ratio of 50: 50 vol.% on silicagel Asch in thermostatted column height 1150 mm and a diameter of 8 mm at a temperature of 25+0.5C, the ratio of sorbent suspension of the sample, equal to 20:1, and further determine the potential content of the raffinate and dewaxed oil in the distillate, as well as the potential content of dewaxed oil in the raffinate by calculation. Speeding up and proselyte by-products of oil on the group hydrocarbon composition and determination of potential content refined, dewaxed oils in heavy distillate fractions, and also to identify potential content in the raffinate dewaxed oil by calculation.

Known methods of analysis of oil on the potential content of distillate and residual oils:

- by the pickup oil fractions, dewaxing, deasphalting and adsorption dividing fractions and residues, consistent mixing of separate groups of hydrocarbons and determining the resulting mixtures of physical and chemical indicators /GOST 11244/.

- defining group of the hydrocarbon composition of the oil fractions by chromatography /Golberg D. O. Control of plant oils and waxes, M-L., Chemistry, 1964, S. 210-222/.

- a rapid method for determining total potential content of base oils in the rest of the oil after extraction of the fractions, wikipaedia to 350oC, including adsorption separation, the dewaxing and, if necessary, a preliminary asphalt destroying balance /Methods of research and analysis of oils and petroleum products. Tr. Its facilities at the Moscow, vol. XVIII, M., 1976/.

method of determining the potential content of oils (PSM) using chromatographic razdelennye method of determining group hydrocarbon composition of the oil: kerosene, gas oil, oil distillate and heavy distillate (350-540oC and above) and deasphalting residues of varying depth selection /Methods of analysis, research and testing of oils and petroleum products. Tr. Its facilities at the Moscow (standard methods), M, 1984, S. 111 - 115/.

The disadvantages of the above methods of analysis is uncomfortable in hardware design, requiring time-consuming, the use of very toxic and harmful solvent is benzene. In addition, they are not the definition of the potential content of refined and dewaxed oils and distillates, as well as the potential content of dewaxed oil in the raffinate.

The closest in technical essence and the achieved results is the adsorption method for the determination of group hydrocarbon composition of petroleum products proposed by M. A. Michian, H. C. Driatzkaya, N. M. Pomace, L. P. Arnbrister, V. I. pomjalovoj /Methods of analysis, research and testing of oils and petroleum products. Tr. Its facilities at the Moscow (standard methods), M, 1984, S. 111 - 115/.

Adsorption method for the determination of group hydrocarbon composition of petroleum products allows you to set the content of paraffin-naphthene, four aromatic groups who bcia adsorbed hydrocarbon is liquid, having a different dielectric constant (petroleum ether with limits of boiling temperatures of 70 - 100oC, benzene and mixtures thereof).

From sorbent is first allocated paraffin-naphthenic hydrocarbons, then aromatic hydrocarbons with increasing number of cycles and resinous substances. Adsorption method for the determination of group hydrocarbon composition is applied to establish the content of individual hydrocarbon groups in kerosene, gas oil, oil distillates, and heavy distillates (350-540oC and above) and deasphalting residues of varying depth selection.

For paraffin-naphthene hydrocarbons are fractions with a refractive index of not more than 1,49.

Aromatic hydrocarbons (a mixture of aromatic hydrocarbons and heteroaromatic compounds) is divided into 4 groups according to conventionally accepted values for the refractive index. I include fractions, obtained after the extraction of paraffin-naphthene hydrocarbons with a refractive index of from 1.49 to 1,53; II - from 1.53 to 1.55V; III - from 1.55V to 1,59; IV over 1,59.

For individual distillates after sampling fractions with a refractive index of more than 1,59 decrease values for the last

To resinous substances include fractions, which because of the dark color it is impossible to determine the refractive index.

On the basis of data obtained sum up the balance of the adsorption separation. The divergence between the two parallel definitions group hydrocarbon composition adsorption method should not exceed 2%.

The disadvantages of this method are:

- use as a solvent of benzene is very harmful and toxic substances;

- identify potential content of the raffinate and dewaxed oil distillate fractions, as well as the potential content of dewaxed oil in the raffinate is not given.

The aim of the present invention is to develop a faster, more convenient in hardware design using less toxic solvents method of analysis of heavy distillate fractions in the group hydrocarbon composition and identification of potential content of refined and dewaxed oils and distillates, as well as the potential content of dewaxed oil in the raffinate.

The problem is solved as follows:

At the first stage out departing on the installation of selective treatment of the distillate N-organic, under the following conditions: as a solvent for separation of the solid hydrocarbon, a mixture of methyl ethyl ketone-toluene (55-60 : 40-45 vol%). The ratio of distillate : the solvent is taken equal to 1 : 4, and the raffinate : solvent 1 : 6 by weight; temperature minus 27-28oC, the cooling rate of 1-2oC/min

Selected solid hydrocarbons (GAC) are washed twice with solvent in the amount of 1:1 by weight to the analyzed sample. The solvent from the solution and GACA distilled at a temperature not exceeding 110oC to constant mass balance.

Determine the content of GACA (G) in distilled water

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where m1- lots of Gaza, g,

m is the mass of a sample of the distillate,

In the second stage, carry out the separation of the residue on a separate dewaxing hydrocarbon group: naphthene - paraffin, 4th aromatic and resin - adsorption-desorption method on silica gel using different solvents: petroleum ether, toluene and mixtures thereof.

Adsorptive separation is performed on silica gel brand Asch in thermostatted column height 1150 mm and a diameter of 8 mm

The method is as follows:

thermally adsorption number of the analytical balance (macroporous silica gel).

Selected process conditions the division of samples : temperature desorption 250,5oC, the ratio of sorbent : hanging = 20 : 1 by weight.

Hitch dewaxed sample (m2~ 1,5 0.0001 g) was dissolved in 5 ml of petroleum ether with limits of boiling temperatures of 40-70oC. In a column Packed with silica gel, to soak filled with petroleum ether (70 ml). Set speed selection solution is not higher than 1 ml/min, and then, when the level of petroleum ether above the sorbent will remain ~ 5 mm, the column entered the test sample. To separate individual hydrocarbon groups consistently introduced first petroleum ether, and then mixed solvents in the amount indicated in the table. 1.

From the bottom of the adsorption column are selected solutions in tubes of 25 ml volume of 10 ml, of which Argonauts solvent at a temperature not exceeding 110oC, and measured the refractive index of the residue. Then the samples are grouped by the refractive index of the hydrocarbon group:

paraffin-naphthenic with nd20< 1.49

and the 4th group of aromatic hydrocarbons and their heteroskedastic:

1 gr. with nd20= 1,49 - 1,53

2 gr. with nd20= 1,53 - 1.55V

3 gr. with nd20= 1, the hydrocarbon group.

The percentage of individual hydrocarbon groups in the original distillate (Cn), or raffinate, calculated by the formula:

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where m1- the weight of a hydrocarbon group, g;

m0- weight of dewaxed sample, ,

The potential of the raffinate in the original distillate (Pthe RAF.) is calculated as the sum of

Pthe RAF.= (G + CP-N+ C1G.arene.), wt.%. (3)

where CP-N- the content of paraffin-naphthene hydrocarbons, calculated by the formula (2), wt.%;

WITH1G.arene.the content of aromatic hydrocarbons of the 1st group, including heteroskedastic with nd20not above 1.53 wt.%.

The potential content of dewaxed oil in the original distillate (PD/Mindistillate) are calculated according to the formula

PD/Mindistillate= (CP-N+ C1G.arene.), wt.%. (4)

The potential content of dewaxed oil in the raffinate (PD/Minthe raffinate) are calculated according to the formula

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Examples of execution.

Example 1. A portion (~ 50

0.01 g) of distillate 1 with limits of boiling points 360-420oC, or 2 distillate with limits of boiling points e minus 28oC. the Precipitated crystals of solid hydrocarbons (GACA) separate the filter from the solvent and washed twice with cooled to minus 28oC mixed solvent (1:1 by weight to the hitch distillate.

Of the selected solution and gacha the solvent is distilled off at a temperature not exceeding 110oC to constant mass balance.

Determine the content of GACA in the distillate by the formula (1).

Adsorptive separation is carried out in controlled adsorption column N 2 with the size specified in the prototype, on silica gel brand Asch, dried at 160 5oC at a temperature of desorption 25 0,5oC, the ratio of sorbent : hanging = 20 : 1.

A portion of dewaxed sample (~ 5 0.0001 g) was dissolved in 15 ml of petroleum ether. In a column filled with silica gel to wet pour petroleum ether (300 ml) with limits of boiling temperatures of 40-70oC. Set the sample rate of the solution is not higher than 2 ml/min, and then, when the level of petroleum ether above the sorbent will remain ~ 5 mm, make a test sample. To separate individual hydrocarbon groups consistently enter first petroleum ether, and then mixed solvents in the amount indicated in the table. 1.

oC, and measure the refractive index of the residue. Then samples unite the refractive index in the hydrocarbon group.

Calculate the content of individual hydrocarbon groups in the original distillate on a column of N 2 by the formula (2).

Potential content refined in the distillate are calculated according to the formula (3), the potential content of dewaxed oil in the distillate and the raffinate, respectively, by the formulas (4) and (5).

The results of the analysis of the distillate and of the raffinate group hydrocarbon composition and calculated data on the potentials presented in table. 2

Example 2.

A portion (~ 50 0.01 g) of distillate 1 with limits of boiling points 360-420oC dissolved (200 0,01) g of a mixture of methyl ethyl ketone : toluene (55-60 : 40-45% vol.) and deparaffinized under the conditions specified in example 1.

Of the selected solution and gacha the solvent is distilled off at a temperature not exceeding 110oC to constant mass balance.

Determine the content of GACA in the distillate by the formula (1).

Adsorptive separation is carried out in controlled adsorption column N 1 (height 1150 mm and diameter 8 mm) on silica gel brand Asch, dried at 160 5oC when the temperature decarbonator in 5 ml of petroleum ether with limits of boiling temperatures of 40-70oC. In a column filled with silica gel to wet pour petroleum ether (70 ml). Set the sample rate of the solution is not higher than 1 ml/min, and then, when the level of petroleum ether above the sorbent will remain ~ 5 mm, column make the sample. To separate individual hydrocarbon groups consistently enter first petroleum ether, and then mixed solvents in the amount indicated in the table. 1.

From the bottom of the adsorption column select solutions in tubes of 25 ml volume 10 ml, from which the solvent is distilled off at a temperature not exceeding 110oC, and measured the refractive index of the residue. Then the samples are combined using the refractive index in the hydrocarbon group.

Calculate the content of individual hydrocarbon groups in the original distillate 1 by the formula (2).

Potential content refined in the distillate are calculated according to the formula (3), the potential content of dewaxed oil in the distillate and the raffinate, respectively, by the formulas (4) and (5).

The results of the analysis of the distillate 1 group hydrocarbon composition on the specified column (N 1) and calculated data on the potentials presented in table. 2

Example 3.

A portion (~ 50 0.01 g) di: 40-45% vol.) and deparaffinized when conditions (see example 1).

Of the selected solution and solid hydrocarbons is distilled at a temperature not exceeding 110oC solvent to a constant weight of the residue.

Determine the content of GACA in the distillate by the formula (1).

Adsorptive separation is carried out in controlled adsorption column No. 1 on silicagel USCG under the conditions specified in example 2.

To separate individual hydrocarbon groups consistently enter first petroleum ether, and then mixed solvents in the amount indicated in the table. 1.

Calculate the content of individual groups of hydrocarbons in the original distillate by the formula (2). The results of the analysis of the distillate 2 group hydrocarbon composition on the specified column (N 1) and calculated data are presented in table. 2

Example 4.

A portion (~ 50 0.01 g) of the raffinate 1 with limits of boiling points 360 - 420oC dissolved (300 0,01) g of a mixture of methyl ethyl ketone : toluene (55-60 : 40-45% vol.) and deparaffinized at a temperature of minus 28oC. the Precipitated crystals of GACA separate the filter from the solvent and washed twice with cooled to minus 28oC mixed solvent taken in quantity (100 0,01) ,

From selected restorea.

Determine the content of GACA in the raffinate 1 by the formula (1).

Adsorptive separation is carried out in controlled adsorption column N 2 (with dimensions of the prototype) on silica gel brand USCG under the conditions specified in example 1.

To separate individual hydrocarbon groups sequentially in the column is introduced first, petroleum ether, and then mixed solvents in the amount indicated in the table. 1.

Calculate the content of individual hydrocarbon groups in the initial raffinate 1 by the formula (2). The results are shown in table.2.

Example 5.

A portion (~ 50 0.01 g) of the raffinate 2 with limits of boiling points 420-490oC dissolved (300 0,01) g of a mixture of methyl ethyl ketone : toluene (55-60 : about 40-45. %) and deparaffinized when conditions (see example 4). Of the selected solution and solid hydrocarbons is distilled at a temperature not exceeding 110oC solvent to a constant weight of the residue.

Determine the content of GACA in the distillate by the formula (1).

Adsorptive separation is carried out in controlled adsorption column N 2 on silica gel brand USCG under the conditions specified in example 1.

The composition and amount of solvents needed to isolate individual p is finite 2 are calculated according to the formula (2). The results are shown in table.

Thus, it is revealed that the potential content of the raffinate in the distillate oil fractions with boiling points 360-420 and 420-490oC can be calculated as the sum of the contents of Gaza, paraffin-naphthene and the 1st group of aromatic hydrocarbons, including geterosoedineniya, with nd20not above 1.53, wt.%

Comparison of the potential presence of solid hydrocarbons, Dept. oils and refined obtained by analysis of the distillate and refined experimentally and by calculation of the potential content refined in the distillate. The results are close (table. 2). The difference lies within the error of analysis, which is less than 3.5 wt.% and in terms of oil does not exceed 0.5%.

The correctness of the obtained results confirmed by the analysis of physico-chemical properties of the base oils compounded by mixing paraffin-naphthenic and aromatic hydrocarbons 1-th group, selected by N columns 1 and 2 of the distillate with outside temperatures of boiling 360-420 and 420-490oC. They are similar in kinematic viscosity, refractive index, viscosity index (VI) (PL. 3).

It should be noted that the analysis of samples on EMA as column N 2 - 14 hours, and according to GOST 11244 this analysis takes about 50 hours.

This technique can be used as a rapid method for the determination of the group hydrocarbon composition of heavy distillate fractions. The accuracy of his matches exactly GOST 11244, and the duration reduced by approximately 5 times.

The method of determining the group of the hydrocarbon composition of the heavy distillate fractions, characterized in that the desorption separate hydrocarbon groups of dewaxed residue distillate or raffinate is conducted sequentially solvents: petroleum ether with limits of boiling temperatures of 40-70oC, a mixture of petroleum ether and toluene, taken in the ratio of 95 : 5 to 75 : 25 vol.%, toluene, alcohol-toluene mixture, taken in the ratio of 50 : 50 vol.%, on silicagel Asch in thermostatted column height 1150 mm and a diameter of 8 mm at a temperature of 25 0,5oC, the ratio of sorbent suspension of the sample is equal to 20 : 1, determine the potential content of the raffinate (Pthe RAF.and dewaxed oil distillates (PD/Mindistillate), as well as the potential content of dewaxed oil refined (PD/MinRAFN/Mindistilate= (CP-N+ C1Gr.arene), wt.%

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< / BR>
where m1- lots of Gaza, g:

m is the mass of a sample of the distillate, g;

mi- the weight of a hydrocarbon group, g;

m0- the weight of dewaxed sample, g;

The content of GACA in the distillate, g, defined by dewaxing using a mixed solvent of methyl ethyl ketone-toluene in the ratio of 55 to 60 : 40 to 45 vol.%;

CP-N- the content of paraffin-naphthene hydrocarbons, wt.%;

C1Gr.arene.the content of aromatic hydrocarbons of the 1st group, wt.%.

 

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