Production of gasoline using stable gas condensate and Zeoforming

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Production of gasoline using stable gas condensate and Zeoforming process products as blending components Nataliya Belinskaya, Andrey Altynov, Ilya Bogdanov, E. V. Popok, Maria Kirgina, and David S.A. Simakov Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.9b00591 • Publication Date (Web): 23 Apr 2019 Downloaded from http://pubs.acs.org on April 25, 2019

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Energy & Fuels

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Production of gasoline using stable gas condensate and Zeoforming process

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products as blending components

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Nataliya Belinskaya1*, Andrey Altynov1, Ilya Bogdanov1, Evgeniy Popok1, Maria Kirgina1,

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David S. A. Simakov2* 1

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National Research Tomsk Polytechnic University, Lenin Avenue 30, Tomsk 634050, Russia

Department of Chemical Engineering, University of Waterloo, Waterloo ON N2L 3G1, Canada

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Abstract

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Zeolites are used as catalysts for a wide range of industrial processes. Due to their microporous

10

structure the use of zeolites is limited to transformation of light feedstocks. At the same time,

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light products of oil extraction such as stable gas condensate are burned or returned to the oil

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reservoir for maintaining reservoir pressure, not being used as a feedstock for the secondary

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refinery. This work considers the use of the stable gas condensate as a feedstock for the

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Zeoforming process and the use of the obtained product as one of the blending components of

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commercial gasoline. After measuring main physicochemical properties and performance

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characteristics of the stable gas condensate, the Zeoforming process was implemented at a

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laboratory scale. The use of the stable gas condensate and Zeoforming products as blending

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components of gasoline was assessed. Applying the software program, recipes for the blending

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of gasoline were developed. It has been found that the Zeoforming process increases the octane

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number of the stable gas condensate, allowing for reduction of the gasoline production costs due

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to replacement of expensive additives.

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Keywords: stable gas condensate; gasoline; blending; zeolite; Zeoforming; octane number

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* Corresponding authors: Tel.: +1 519 888 4567 ext. 37048; E-mail addresses: [email protected], [email protected]

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1. Introduction

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According to statistics [1], global gas flaring constitutes about 140 billion cubic meters per year.

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Russia remains the world's largest gas flaring country, with the amount of flared associated

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petroleum gas of 21.2 billion cubic meters [2]. Due to environmental aspects, specifically

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reducing green house gas emissions globally, it is required that by-products of crude oil

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extraction, such as associated petroleum gas and gas condensate, are utilized to avoid pollution

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caused by flaring [3]. Moreover, increasing annual consumption of automotive fuels as an energy

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source for internal combustion engines forces manufacturers to look for alternative ways of their

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production.

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Stable gas condensate is a mixture of liquid hydrocarbons (C5+) obtained from gas

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condensate, after the removal of dissolved gases during gas and oil fields exploitation [4].

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Typically, stable gas condensate consists of gasoline, kerosene and, to a lesser extent, higher-

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boiling fractions. The hydrocarbon composition varies significantly, depending on the location

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and conditions of extraction. At the moment, the most promising ways to utilize this valuable

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feedstock is to use it for petrochemicals production, and a blending component of motor fuels for

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gasoline blending applications [5–11]. Quality indicators such as octane number, density,

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saturated vapor pressure, fractional composition, as well as the content of sulfur, benzene,

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aromatics and olefins are strictly regulated [12,13].

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In this work we suggest to use zeolites for upgrading stable gas condensate via Zeoforming

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process, to make it a suitable blending component for commercial gasoline production [14-25].

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Zeolites are microporous aluminosilicates which are used in a variety of industrial

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applications [14] due to several advantages, such as low operational costs and capital

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investments, simplicity of the technology (in terms of catalyst synthesis and process design),

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safety requirements with regards to explosion and fire hazards, and low sensitivity to the

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feedstock quality [15]. Zeolites are widely used as ion-exchangers [16,17] and as shape-selective

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heterogeneous catalysts, especially in petroleum refining industry, hydrocracking [18] and ACS Paragon Plus Environment

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hydrodewaxing [19],

linear

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isomerization [22],

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hydrodeoxygenation [25].

alkyl

benzene

aromatization [23,24],

synthesis [20],

methanol

to

catalytic

hydrocarbons

cracking [21],

conversion,

and

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The Zeoforming process is aimed to improve octane number of gasoline fractions. In this

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case, due to their unique structure, molecular-sieve and acid properties, zeolites show high

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activity and selectivity towards reactions of dehydrogenation, isomerization, cracking,

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oligomerization, and dehydrocyclization of organic molecules [26–32]. In comparison to

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conventional reforming of gasoline fractions, Zeoforming does not require the use of

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hydrogen [33,34]. Another advantage is that Zeoforming is not sensitive towards catalytic

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poisons, such as sulfur compounds, which are always present in petroleum fractions [35]. There

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are numerous works dedicated to the gasoline blending technology [36–38] and various

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petroleum refining processes using zeolite catalysts [15–35]. However, there is lack of research

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on the use of the stable gas condensate (unprocessed and upgraded via Zeoforming) as one of the

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blending components of commercial gasoline.

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The aim of this work was to evaluate the use of the unprocessed and upgraded (via

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Zeoforming) stable gas condensate as one of the blending components of commercial gasoline. It

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was found that the upgraded stable gas condensate produces a high quality gasoline, having

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research octane number (RON) 92, 95 and 98. The conversion of hydrocarbons constituting the

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stable gas condensate on a zeolite catalyst (in the Zeoforming process) was analyzed and the

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influence of various technological parameters on the composition and properties of the

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Zeoforming products was established. The ultimate goal of our research is to resolve the

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problems of meeting the demand for automotive fuels and utilizing by-products of oil fields

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exploitation.

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2. Materials and methods


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Four samples of stable gas condensate were obtained from one of the oil fields in Western

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Siberia, Russia. Samples were assigned numerical ciphers from 1 to 4.

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For each sample, the following properties were determined:

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 Sulfur content was determined using a “Spectroscan S” analyzer according to

81

ASTM D4294-16 “Standard test method for sulfur in petroleum and petroleum products

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by energy dispersive X-ray fluorescence spectrometry” [39];

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 Density at 15 C was determined using a Stabinger viscometer SVM3000 Anton Paar

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according to ISO 3675:1998 “Crude petroleum and liquid petroleum products.

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Laboratory determination of density. Hydrometer method” [40];

86 87



Fractional composition was determined according to ISO 3405:2011 “Petroleum products. Determination of distillation characteristics at atmospheric pressure” [41].

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Hydrocarbon composition of the stable gas condensate and the products of the Zeofoming

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process was determined by the gas-liquid chromatography method using a Chromatec-

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Crystal 5000 chromatograph with a quartz capillary column 25 m × 0.22 mm, stationary phase –

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SE-54, carrier gas – helium according to EN 14517:2004 “Liquid petroleum products –

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Determination of hydrocarbon types and oxygenates in petrol – Multidimensional gas

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chromatography method” [42]. To calculate the research octane number (RON), motor octane

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number (MON), saturated vapor pressure (SVP) was used [43,44].

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3. Experimental

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Laboratory implementation of the Zeoforming process was carried in a catalytic reactor unit

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manufactured by the “CATACON” company (Fig. 1).


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Fig. 1. Schematic of the laboratory catalytic reactor unit

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The unit is able to operate at the maximum pressure of 90 bar and maximum temperature

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of 700 °C. The reactor block consists of the reactor (Fig. 2), electric heating element and check

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valve system. The reactor is a stainless steel pipe with the internal diameter of 12 mm equipped

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with the controlling thermocouple located in the catalyst bed.

104 105

Fig. 2. Catalytic reactor scheme

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The product separation block consists of the uniflow cooler and high-pressure separator.

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After separation of the products, condensate is drained through the valve to the condensate


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receiver. Gas products leave the high pressure separator through the side valve and are sent to the

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analytical control block.

110 111

Specifications of the catalytic unit are shown in Table 1. Table 1. Specifications of the catalytic unit Specification

Value

Maximum pressure, bar

90

Reactor type

flow-type reactor

Temperature range of the reactor, °С

50–700

Catalyst grain size, mm

0.5–2.0

Internal diameter of the reactor, mm

12.0

Hydrogen consumption range, ml/min

10–500

Liquid consumption range, ml/min

0.01–9.99

Voltage feed, V 112 113

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The Zeoforming process was implemented using the KN-30 zeolite catalyst. The characteristics of the catalyst are shown in Table 2. Table 2. Catalyst characteristics

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Structure type Weight content of zeolite, %

ZSM-5 not less than 80

Weight content in zeolite powder, % SiO2

90.0–97.6

Al2O3

1.4–2.7

Na2O

not more than 0.1

Fe2O3

0.35–1.25

Pellet diameter, mm Specific surface area, m2 Bulk density, g/sm3


3.0–4.3 300 0.60–0.86

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The main advantages of the catalyst KN-30 include: resistance to catalytic poisons; lack of

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precious metals in the content; the catalyst is environmentally friendly and easily recyclable; the

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possibility of production at any catalyst plant under the control of the licensor; the approximate

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ratio of the required mass of catalyst to feedstock is 0.2 kg per 1 ton.

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The volume of the catalyst was 10 cm3. At the preliminary preparation stage, the catalyst

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was grinded and sieved to prepare particles of 0.5–1.0 mm in size. After the grinding, the

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catalyst was loaded into a flow-type reactor and was activated in order to remove adsorbed

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moisture and organic matter from the surface. During activation, the catalyst was subjected to

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calcination for 5 hours at the temperature of 500 °C in the flow of nitrogen-air mixture.

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As the feedstock, stable gas condensate (sample No. 4) was used.

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7 test runs were carried out in the conditions of varying technological parameters of the

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Zeoforming process, such as temperature, pressure, and feedstock space velocity (Table 3). Table 3. Technological conditions of the laboratory test runs

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Feedstock space Test

Temperatures, °C

Pressure, MPa velocity, ml/min

No.1

375

2.5

0.33

No.2

400

2.5

0.33

No.3

425

2.5

0.33

No.4

400

3.5

0.33

No.5

400

4.5

0.33

No.6

400

2.5

0.5

No.7

400

2.5

0.67

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130 ACS Paragon Plus Environment

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4. Results and discussions

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4.1. Properties and composition of stable gas condensate samples

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The values of density and sulfur content determined for stable gas condensate samples are

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presented in Table 4. Table 4. Sulfur content in stable gas condensate samples

135

Stable gas condensate sample

1

2

3

4

Sulfur content, ppm

33

28

30

17

Density at 15 °C, g/cm3

0.666 0.657 0.719 0.674

136 137

The average sulfur content in the samples of stable gas condensate accounts for 27 ppm.

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This indicates the possibility of using stable gas condensate as the component for the production

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of the 4th ecological class gasoline. Moreover, if low-sulfur components (reformate, aromatic

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hydrocarbons, isomerizate) are included in gasoline production, it is possible to produce gasoline

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of the 5th ecological class (the maximum sulfur content according to [13] for the 4th ecological

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class is 50 ppm, for 5th ecological class it is 10 ppm, respectively).

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The density of stable gas condensate samples is close to the density of conventional

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gasoline components, such as alkylate or straight-run gasoline and the average value is

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0.679 g/cm3.

146 147

Table 5 shows fractional composition of stable gas condensate samples. Table 5. Fractional composition of stable gas condensate samples Stable gas condensate sample Volume, %

1

2

3

4

T, °C IBP

28.4

30.1

27.6

29.0

10

39.3

40.4

35.9

43.0


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44.0

45.5

40.5

46.0

30

49.0

51.0

45.6

52.0

40

54.6

56.8

51.2

56.0

50

60.9

63.2

57.1

61.0

60

68.0

70.6

64.4

66.0

70

76.7

79.4

73.1

77.0

80

87.1

90.9

84.5

85.0

90

105.2

112.9

103.4

95.0

EBP

138.5

149.6

139.9

117.0

148

IPB – initial boiling point; EPB – end boiling point.

149

The fractional composition of the studied gas condensate samples has values close to the

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fractional composition of straight-run gasoline widely involved in the production of commercial

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gasoline.

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Group hydrocarbon composition of stable gas condensate samples are presented in Fig. 3.

153 154

Fig. 3. Hydrocarbon composition of stable gas condensate samples


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The results of chromatographic analysis of stable gas condensate samples (Fig. 3) show

156

that in stable gas condensate the hydrocarbon groups of paraffins, isoparaffins and naphthenes

157

predominate.

158

The content of olefins in the samples is in the range 0.24-3.08 % vol., which does not

159

exceed the allowable values in gasoline, according to [12] (not more than 18.0 % vol.). The

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content of aromatic hydrocarbons is minimal; it lies in the range of 0.18-0.62 % vol., while the

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regulated content of aromatic hydrocarbons, according to [12] is not more than 35.0 % vol. for

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all gasoline grades. It is also worth noting that the benzene content in all samples does not

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exceed 0.2 % vol. (Table 6), which satisfies the requirements imposed by [13] for gasoline of the

164

5th ecological class (not more than 1 % vol.).

165 166

Characteristics of stable gas condensate samples, calculated using “Compounding” software program, are presented in Table 6. Table 6. Characteristics of stable gas condensate samples

167

Stable gas condensate sample Characteristic 1

2

3

4

RON

69.4

69.8

70.6

66.4

MON

66.6

67.6

67.8

63.2

SVP, kPa

104.3

93.7

97.4

71.36

Density at 15 °C, kg/m3

661.7 659.4 666.1 677.6

Benzene content, % vol.

0.14

0.17

0.15

0.17

Aromatic hydrocarbons content, % vol.

0.58

0.18

0.57

0.62

Olefins content, % vol.

0.14

3.07

1.86

1.14

168 169

From the results presented in Table 6, it follows that the average research octane number of

170

stable gas condensate samples is 69.1 points, which is 10 points higher than the average research

171

octane numbers of straight-run gasoline (50-60 points).


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The saturated vapor pressure for the samples of stable gas condensate averages 91.7 kPa,

173

which implies that the use of stable gas as one of the blending components of gasoline is most

174

suitable for the production of winter fuel. This is due to the fact that according to [12], the

175

regulated value of the saturated vapor pressure of gasoline in summer time is 35-80 kPa, in

176

winter and off-season time is 35-100 kPa.

177

Based on the obtained results, it follows that the use of stable gas condensate as one of the

178

blending components of gasoline is possible. In addition, this feedstock is characterized by a

179

large margin of content of olefin, aromatic hydrocarbons and benzene, which makes stable gas

180

condensate a promising component in the production of gasoline. However, because of

181

comparably low octane number of stable gas condensate, using this component as a blending

182

component of gasoline require involving larger amount of high octane more expensive

183

components, such as toluene, MTBE. Catalytic upgrading of stable gas condensate is more

184

sustainable.

185

4.2. The effect of reaction temperature on the composition and properties of

186

Zeoforming products

187

Group composition of the Zeoforming products obtained at various process temperatures

188

(375 °C, 400 °C, 425 °C) are presented in Fig. 4.


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189 190

Fig. 4. Group hydrocarbon composition of the Zeoforming products depending on the process

191

temperature

192 193 194

The characteristics of the Zeoforming products, calculated using the “Compounding” software program, are presented in Table 7. Table 7. Characteristics of the Zeoforming products depending on the process temperature Process temperature Characteristic 375 °C 400 °C 425 °C RON

82.5

84.2

87.4

MON

77.3

77.5

79.5

SVP, kPa

123.6

97.7

108.4

Density at 15 °С, kg/m3

690.4

738.8

732.7


0.07

3.49

4.17


10.26

24.07

25.25


4.81

4.31

3.62

195


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As it can be seen from the results presented in Fig. 3, maximum content of isoparaffins and

197

minimum content of olefins are common for the products obtained at different temperatures. As

198

the process temperature increases, the content of aromatic hydrocarbons, including benzene

199

(Table 7), increases. This is due to increase in the rate of target reaction of aromatization. As for

200

saturated vapour pressure and density (Table 7), the Zeoforming product obtained at 400 oC is

201

characterized by maximum density and minimum saturated vapour pressure. This is due to

202

higher content of light n-paraffins and isoparaffins in the product.

203

From Table 7, it follows that the implementation of the Zeoforming process allows

204

increasing the octane number of stable gas condensate. Specifically, the research octane number

205

is increased by 16.1 points at the process temperature of 375 °C; by 17.8 points at the process

206

temperature of 400 °C, and by 21 points at the process temperature of 425 °C. Octane number of

207

the Zeoforming products is as higher as more aromatic hydrocarbons content is observed. The

208

increase in octane number makes the Zeoforming product a promising blending component for

209

the production of gasoline. Moreover, from Table 7, it follows that the Zeoforming product,

210

obtained at the temperature of 375 °C, is the most appropriate blending component for

211

production of gasoline, because it is characterized by a relatively high octane number and low

212

benzene content.

213

In case when, the process temperature increases, the content of benzene in the products

214

rises and exceeds the values permissible for gasoline (not more than 1 % vol.), which makes

215

them inappropriate to use as the blending components for gasoline production.

216

4.3. The effect of pressure on the composition and properties of Zeoforming

217

products

218

Group composition of the Zeoforming products obtained at various pressures (2.5 MPa, 3.5 MPa,

219

4.5 MPa) are presented in Fig. 5.


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Fig. 5. Group hydrocarbon composition of the Zeoforming process product depending on the

222

pressure

223 224 225

The characteristics of the Zeoforming products, calculated using the “Compounding” software program, are presented in Table 8. Table 8. Characteristics of the Zeoforming products depending on the pressure Process pressure Characteristic 2.5 MPa 3.5 MPa 4.5 MPa RON

84.2

85.8

89.1

MON

77.5

79.4

81.1

SVP, kPa

97.6

149.3

182.5


738.8

706.0

710.6


3.49

3.43

3.15


24.07

20.14

19.98


4.31

6.73

3.04

226


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As it can be seen from the results, presented in Fig. 5, the predominate group of

228

hydrocarbons in the product differs depending on the pressure. N-paraffins predominate in the

229

product, obtained at 3.5 MPa, while at 2.5 MPa and 4.5 MPa the content of isoparaffins is

230

maximum. Moreover, at 2.5 MPa and 4.5 MPa the content of olefins is minimum, while at

231

3.5 MPa the content of naphthenes is minimum. As the pressure increases, aromatic

232

hydrocarbons content, including benzene (Table 8), decreases. This is due to decrease in the

233

selectivity of paraffins conversion to aromatic hydrocarbons as far as high pressure is

234

advantageous for side cracking reactions. As it can be seen from results presented in Table 8,

235

increase in the pressure of the process saturated vapour pressure of the Zeoforming products

236

increases. The opposite tendency is observed for density. This is due to decrease in the content of

237

heavy aromatic hydrocarbons.

238


239


240

is increased by 17.8 points at the process pressure of 2.5 MPa; by 19.4 points at the process

241

pressure of 3.5 MPa, and by 22.7 points at the process pressure of 4.5 MPa. In spite of decrease

242

in aromatic hydrocarbons content in the Zeoforming products, the octane number increases due

243

to increase in high octane light n-paraffins and isoparaffins content. In the context of involving

244

in gasoline production, the products, obtained at higher pressure, are the most preferable,

245

because they have high octane number and low content of aromatic hydrocarbons which is

246

limited in gasoline. However, involving these components in gasoline production is limited by

247

high content of benzene.

248

4.4. The of space velocity on the composition and properties of Zeoforming

249

products

250


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Group composition of the Zeoforming products obtained at various feedstock space velocities

252

(0.33 ml/min, 0.5 ml/min, 0.67 ml/min) are presented in Fig. 6.

253 254

Fig. 6. Group hydrocarbon composition of the Zeoforming process products depending on the

255

feedstock space velocity

256 257

The characteristics of the Zeoforming products, calculated using the “Compounding” software program, are presented in Table 9.

258

Table 9. Characteristics of the Zeoforming process products depending on the feedstock space

259

velocity Feedstock space velocity Characteristic 0.33 ml/min 0.5 ml/min 0.67 ml/min RON

84.2

88.2

88.8

MON

77.5

82.5

83.0

SVP, kPa

97.7

167.0

190.4


738.8

687.4

688.5


3.49

2.43

0.08


24.07

16.28

12.7


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Energy & Fuels


4.31

4.44

6.33

260 261

As it can be seen from the results, presented in Fig. 6, maximum content of isoparaffins is

262

common for all products. Simultaneously, minimum olefins content is observed at feedstock

263

space velocities 0.33 ml/min and 0.67 ml/min, while at 0.5 ml/min the content of naphthenes is

264

minimum. As the feedstock space velocity increases, the content of aromatic hydrocarbons,

265

including benzene (Table 9), decreases. This is due to decrease in the residence time and as a

266

result, decrease in the depth of aromatization. As is can be seen from the results, presented in

267

Table 9, as the feedstock space velocity increases, saturated vapour pressure of the Zeoforming

268

products increases, while the density decreases. This is due to decrease in the content of heavy

269

aromatic hydrocarbons.

270


271


272

is increased by 17.8 points at the feedstock consumption rate of 0.33 ml/min; by 21.8 points at

273

the feedstock consumption rate of 0.5 ml/min, and by 22.4 points at the feedstock consumption

274

rate of 0.67 ml/min. In spite of the decrease in aromatic content in the Zeoforming products with

275

decreasing feedstock space velocity, octane number of the products increases due to increase in

276

the content of high octane light n-paraffins and isoparaffins. In the context of involving in

277

gasoline production, the products, obtained at higher feedstock space velocities, are the most

278

preferable, because they have high octane number and low content of aromatic hydrocarbons and

279

benzene which are limited in gasoline.

280

4.5. Developing the recipes for gasoline blends using the stable gas condensate

281

as a blending component

282

With the use of the software program “Compounding”, recipes for blending gasoline 92 RON

283

(commercial grade gasoline having RON 92) and 95 RON (commercial grade gasoline having


17

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 18 of 30

284

RON 95) grades were developed. Toluene and methyl tertiary butyl ether (MTBE) were used as

285

the additional blending components. These components were chosen due to their high octane

286

numbers, availability and relatively low price. The results of calculating the characteristics of

287

MTBE and toluene using the software program “Compounding” are presented in Table 10. Table 10. Characteristics of the additional blending components

288

Characteristic

Toluene MTBE

RON

120.0

124.4

MON

103.3

109.5

7.6

40.3


867.3

735.0


0.47

0.00


97.26

0.01


0.58

0.44

SVP, kPa

289

The developed recipes for gasoline blending are presented in Table 11.

290

Table 11. Recipes for blending gasoline 92 RON and 95 RON grades using stable gas

291

condensate as one of the components Gasoline grade Content, % wt. 92 RON Stable gas condensate sample

95 RON

1

2

3

4

1

2

3

4

Stable gas condensate

59.5

61.5

61.0

56.5

53.5

55.5

55.5

51.0

MTBE

9.0

9.0

9.0

9.0

12.5

12.0

12.0

14.5

Toluene

31.5

29.5

30.0

34.5

34.0

32.5

32.5

34.5

292 293 294

The characteristics of gasoline, obtained by the developed recipes, were also calculated using the “Compounding” software program. The results are presented in Table 12.

295


18

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296

Energy & Fuels

Table 12. Characteristics of gasoline blends obtained according to the developed recipes Characteristic

92 RON

95 RON Regulation

Stable gas

value for

1

2

3

4

1

2

3

4

RON

92.0

92.0

92.2

92.2

95.2

95.2

95.1

95.2

92.0/95.0

MON

83.8

84.4

84.2

83.3

86.1

86.7

86.3

85.7

83.0/85.0

condensate

92 RON/95 RON

sample

SVP, kPa

68.1

63.5

65.3

46.6

63.4

59.3

61.4

44.9

35-801 35-1002

Density at 733.1 727.5 732.7 748.2 740.8 736.0 739.8 751.4 15 °С,

725.0-780.0

kg/m3

Sulfur 19.64 17.22 18.30

9.60

17.66 15.54 16.65

8.67

10.003 50.004

content, ppm Benzene 0.19

0.20

0.19

0.24

0.20

0.21

0.19

0.24

1.00

25.88 23.74 24.52 28.94 28.16 26.44 26.77 29.05

35.00

0.28

18.00

content, % vol. Aromatic hydrocarbons content, % vol. Olefins, % vol.

2.24

1.42

0.91

0.29

2.08

1.34

0.88

297

1summer

time; 2winter and off-season time; 35th ecological class; 44th ecological class

298

Table 12 shows that for the production of 92 RON gasoline, the main component is stable

299

gas condensate (the share in the recipe is 56.5-61.5 % wt.). MTBE, as a component with content

300

of esters of C5 and higher, and having a high octane number, is added in the amount of 9 % wt.

301

The regulation content of MTBE in gasoline is no more than 15 % wt. (according to [12]). The

302

content of toluene in gasoline varies within the limits of 29.5-34.5 % wt.


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Page 20 of 30

303

In the recipe for blending gasoline 95 RON, insignificant decrease in the share of stable

304

gas condensate in the mixture volume is observed. Compared with the grade 92 RON gasoline,

305

the share of stable gas condensate decreased by 6 % wt. for all samples of stable gas condensate,

306

simultaneously, the content of MTBE has increased by 3 % wt. (на 5.5% wt. for stable gas

307

condensate No. 4 due to its lower RON). This is due to the higher requirements for the octane

308

number for this grade of gasoline.

309

As it can be seen from the data presented in Table 12, gasoline obtained according to the

310

developed recipes meet all the requirements of [12] and [13], which confirms the possibility of

311

using stable gas condensate as one of the blending component for gasoline production.

312

According to the sulfur content, the obtained gasoline can be related to the 4th ecological

313

class [13] (gasoline, obtained using stable gas condensate No.4, meet 5th ecological class). The

314

average sulfur content in gasoline 92 RON is 16.19 ppm, in the 95 RON grade it accounts for

315

14.63 ppm. Since the obtained gasoline will be used primarily to ensure the own needs of the oil

316

field, the use of gasoline of the 4th ecological class is permissible (the requirements [13] do not

317

apply to fuel which use to ensure own needs on drilling platforms and oil fields).

318

4.6. Developing the recipes of gasoline blends the Zeoforming products as the

319

blending components

320

With the use of the software program “Compounding”, recipes for blending gasoline

321

92 RON and 95 RON grades were developed. As the blending components, stable gas

322

condensate (sample No. 4), toluene and the Zeoforming products (obtained at the process

323

temperature of 375 °C) were used. The developed recipes are presented in Table 13.

324

Table 13. Recipes for blending gasoline 92 RON and 95 RON grades with the use of stable gas

325

condensate and the Zeoforming products as the components Grade Content, % wt. 92 RON 95 RON 98 RON


20

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Energy & Fuels

Stable gas condensate No. 4

19

12

0

Toluene

29

33

33.5

The product of the Zeoforming process (at 375 °С)

52

55

64

MTBE

0

0

2.5

326

The characteristics of gasoline blends, obtained according to the developed recipes, were

327

also calculated using the “Compounding” software program. The results are presented in

328

Table 14.

329

Table 14. The characteristics of gasoline blends, obtained according to the developed recipes Regulation value Characteristic

92 RON 95 RON 98 RON

for 92 RON/95 RON/98 RON

RON

92.4

95.2

98.2

92.0/95.0/98.0

MON

84.3

86.5

89.0

83.0/85.0/88.0

SVP, kPa

80.0

79.0

82.6

35-801 35-1002

Density at 15 °С, kg/m3 Sulfur content, ppm

739.3 3.23

747.3 2.04

750.8 0

725.0-780.0 10.003 50.004


0.19

0.19

0.18

1.00

29.35

33.18

34.63

35.00

3.04

3.18

3.49

18.00

Aromatic hydrocarbons content, % vol. Olefins content, % vol. 330

1summer

time; 2winter and off-season time; 35th ecological class; 44th ecological class

331

As it can be seen from Table 14, the main components of the gasoline are the Zeoforming

332

products for all three grades. Addition 2.5 % wt. of MTBE and excluding unprocessed stable gas

333

condensate provide possibility to produce gasoline 98 RON. Moreover, from Table 14, it can be


21

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 22 of 30

334

seen that gasoline blends obtained according to the developed recipe, meet all the requirements

335

[12] and [13].

336

The sulfur content in gasoline 92 RON grade is 3.23 ppm; in gasoline 95 RON grade it is

337

2.04 ppm; in gasoline 98 RON grade it is 0 ppm. Thus, gasoline, obtained by the developed

338

recipes, can be referred to the 5th ecological class according to [13]. This ecological class makes

339

it possible to use the gasoline not only on the field and throughout the Russian Federation, but

340

also to supply the gasoline for export.

341 342

The obtained results testify to the possibility of using the Zeoforming products (when the process feedstock is stable gas condensate) as one of the blending component of gasoline.

343

It is important to note, that the use of the Zeoforming products in the production of

344

gasoline, completely eliminates the use of MTBE for grades 92 RON и 95 RON and reduces the

345

use of toluene (by 5.5 % wt. for gasoline 92 RON grade and 1.5 % wt. for gasoline 95 RON

346

grade), which in turn will significantly reduce the cost of gasoline production.

347

5. Conclusions

348

The use of the stable gas condensate (unprocessed and upgraded via Zeoforming) as a blending

349

component of gasoline was suggested. For the first time, the authors have analyzed the directions

350

of the stable gas condensate hydrocarbon transformations in the Zeoforming process. The

351

influence of various technological parameters on the composition and properties of the

352

Zeoforming products was established. The recipes for blending gasoline of different grades using

353

the stable gas condensate and the Zeoforming products were developed.

354

The main conclusions of the work are as follows:

355

1. The main physicochemical properties, operational characteristics and hydrocarbon

356

composition of stable gas condensate samples, obtained from one of the fields of Western

357

Siberia, Russia, were experimentally determined. The obtained results testify to the efficiency of


22

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Energy & Fuels

358

using stable gas condensate as the blending component of gasoline, thereby enabling more

359

efficient utilization of the by-products of oil extraction the production motor fuels.

360

2. On the laboratory catalytic unit, using the zeolite catalyst KN-30 and stable gas

361

condensate, the Zeoforming process was implemented. It was shown that implementation of the

362

Zeoforming process allows increasing the research octane number of stable gas condensate

363

(maximum by 22.7 points). The obtained results testify to the possibility of using the Zeoforming

364

process products (when using stable gas condensate as the feedstock) as the blending component

365

of gasoline.

366

3. It was found that with increase in the temperature, decrease in the pressure and

367

feedstock space velocity, the content of aromatic hydrocarbons, including benzene, in the

368

Zeoforming products (when feedstock is stable gas condensate) increases.

369

4. It was established that RON of the Zeoforming products increases with the increase in

370

the process temperature due to increase in the content of aromatic hydrocarbons. RON of the

371

Zeoforming products increases with the increase in the pressure and feedstock space velocity due

372

to increase in the content of high octane light n-paraffins and isoparaffins. However, in this case

373

undesirable increase in saturated vapour pressure and density of obtained products was observed.

374

5. It was established that the most preferred blending component of gasoline is the

375

Zeoforming process product, obtained at the process temperature of 375 °C using stable gas

376

condensate as the feedstock because it is characterized by a relatively high octane number and

377

low benzene content.

378

6. Applying the “Compounding” software program, recipes for blending gasoline grades

379

92 RON, 95 RON with the use of stable gas condensate as the main blending component, and

380

methyl tertiary butyl ether and toluene as additional components were developed. Gasoline

381

blends obtained according to the developed recipes meet all the requirements [12] and [13],

382

belong to the 4th ecological class and can be used to supply the needs of oil fields.


23

Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 24 of 30

383

7. The recipes of gasoline of 92 RON, 95 RON, 98 RON grades with the use of stable gas

384

condensate and the Zeoforming process products as the main blending components were

385

developed. Gasoline obtained according to the developed recipes meet all the requirements of the

386

regulation documents [12,13], belong to the 5th ecological class, that makes it possible to use the

387

gasoline not only on the oil field and throughout the Russian Federation, but also to supply the

388

gasoline for export.

389

6. It was found that the use of the Zeoforming process products in the production of

390

gasoline makes it possible to completely eliminate the use of methyl tertiary butyl ether for

391

grades 92 RON и 95 RON and reduce the use of toluene (by 5.5 % wt. for gasoline 92 RON

392

grade and 1.5 % wt. for gasoline 95 RON grade), which in turn will significantly reduce the cost

393

of gasoline production.

394

The authors have showed that the solution to environmental problems associated with the

395

inefficient utilization of stable gas condensate is possible by using it as an alternative feedstock

396

for gasoline production. It was shown that one of the efficient ways to transform stable gas

397

condensate into gasoline component is the Zeoforming process.

398

Acknowledgements

399

The research was funded by the subsidy for state support of the leading universities of the

400

Russian Federation in order to increase their competitiveness among the world's leading

401

scientific and educational centers and the work was performed within the framework of the state

402

task №10.13268.2018/8.9.


24

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Energy & Fuels

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