Кey Industry Engineering Group s.r.o. offers a technology for production of liquid fuels (gasoline, diesel fuel, dimethyl ether) from synthetic gas using bi-functional catalysts.

This process was developed by Siberian technological company "ZEOSIT". All data published below is developed and presented by ZEOSIT.

There are three classic techniques for converting synthetic gas into a liquid fuel (see the diagram and table 1):

1. The Fisher-Tropsh reaction (F-T) reduces oligomerization of carbon oxide with heterogenic catalysts containing metals of group VIII - Fe, Co and Ru. The final products of the reaction are paraffins, olefins, and oxygen-containing compounds: alcohols, aldehydes, ketones, acids and ethers.
2. The Mobil many-stage process which produces methanol synthetic gas and dimethyl ether (DME).
3. A multi-stage, high content of durene in gasoline cut (TIGAS process).

Main indicators of the processes and compositions of the products of synthetic gas transformation by different routes (industrial and pilot testing data) are shown in Table 1.

Diagram of the major routes of transformation of synthetic gas into liquid diesel fuels

Кey Industry Engineering Group s.r.o. offers a technology for antiknock gasoline and diesel fuel production from synthetic gas using bi-functional catalysts.

1) The one-stage process represents consecutive-parallel reactions (route III of the above diagram):

2) Productivity and selectivity of the process is considerably higher than of the F-T process.

3) Produced gasoline has octane number of 80-93IM with olefin content less than 3% and benzene of 0.2 - 0.8% meeting current international standards.

The KIE one-stage process with bi-functional catalysts is considerably more efficient than the Mobil process. At the same time, high selectivity of gasoline cut is retained, and the output quality complies with national standards for absence of sulfur- and nitrogen-containing compounds and benzene content (less than 0.8% of the mass). Unlike the TIGAS process, KIE's technology controls the content of aromatic hydrocarbons (15 to 40% of the mass), and the content of durene does not exceed 3% of the mass.

Due to these factors the Zeosin process does not require ennobling of liquid diesel fuels. The total weight of equipment used in this process is twice as light (2 to 2.2) as the equipment of other known processes.

Table 1. Major indicators of the processes and compositions of products of transformation of synthetic gas by different routes (industrial and pilot testing data).

Route №	I (Fisher-Tropsh process)			II (Mobil process)		III (bi-functional catalysis)
Products content, % of the mass	Sasol-1а	HTFT (SAS process)b	LTFT (Sasol SPD)b	adiabtic reactorc	"fluid bed"c	Pilot tests
						Option 1d	Option 2e	Option 3h
СН4		7	4			3,1	6,0	1,4
Gaseous hydrocarbons (С1-С2)	20			1,4	5,6
Olefins С2-С4		24	4			0,6	1,1	0,7
Paraffin С2-С4		6	4			10,9	10,2	21,1
Liquid gas (С3-С4)	23			18,7	34,4
Gasoline (С5-С12)	39	36	18	79,9	60,0	73,8	77,7	76,8
Diesel fuel (С13-С18)	5	12	19	0	0	11,6	5,0	0
Fuel oil (С19 and higher)	6	9	48	0	0	0	0	0
Oxygen-containing compounds	7	6	3	0	0	0	0	0
Catalyst productivity on gasoline cut, relative to unit	<1	<1	<1	<3		2	4	5
Gasoline octane number	58 (ММ)	<70 (ММ)	<70 (ММ)	93 (ИМ)	95 (ИМ)	80-93 (ИМ)
Olefin content in gasoline, % of the mass	74-87	70	64	up to 13		up to 3

^а[Sheldon R.A. Chemical products based on synthetic gas /translated form Engl. Ed. S.M. Loktev- М.: Chemistry, 1987],
^b[Jager B., in "Natural Gas Conversion IV" (A. Parmaliana et al. eds), Stud. Surf. Sci. Catal., Amsterdam, 119 (1998), 25-34],
^c[MacDougall L.V., Catalysis Today, 8 (1991) 337-369],
^{d, e, h}process options developed at Scientific research Center "Zeosit", Russian Academy of Science.

Brief description of the Zeosin process for producing gasoline from synthetic gas

Intake

Synthetic gas is supplied to the compressor suction from the natural gas conversion block where it mixes with circulation gas. The mixed gas is further squeezed up to an operating pressure point, and then divided into two streams. The major stream is heated in the heat exchanger-recuperator due to the reactor-heated gas, and is supplied to the reactor inlet. The minor stream -- cold bypass -- goes to the reactor's inter-shelf space for thermal regulation in the reactor.

After passing the reactor, the reaction products are consecutively supplied to the heat exchanger-recuperator and the cooler-condenser, to be cooled by the jacket water.

Separation

Separation of gas from the liquid products of the reaction takes place in the high pressure separator. To prevent accumulation of inert-gases (nitrogen, methane and etc.) in the circulation gas, part of it is removed as relief gas. Relief gas is supplied to the combustion network for production of thermal and electric power. After passing through a high pressure separator, the major portion of gas is supplied to the compressor suction.

After leaving the high pressure separator, liquid products are throttled and separated from the dissolved gas in the low pressure separator, and then are divided into water and unstable gasoline cut in the sludge tank. Water from the sludge tank is supplied to the natural gas conversion block, while unstable gasoline is supplied to the stripping tower where light hydrocarbons are separated from the gasoline cut. Commercial gasoline coming from the bottom of the tower is collected in the tank and is supplied to the storage.

Product composition

The gasoline output makes up 65-70% of the mass of supplied natural gas; about 5% of the natural gas hydrocarbon is transformed into light hydrocarbons (С₃-С₅) that is used for combustion purposes; less than 5% (hydrocarbon) is removed in the form of СО2 and the rest 20-25% of the mass of hydrocarbon are bled-off in the form of untransformed СО, СО₂ and uncondensed С₁ - С₄ hydrocarbons. Relief gases are utilized in the gas turbine power plant (ГТУ) for generation of thermal and electric power.

Olefin content in the gasoline is less than 3%. Benzene content does not exceed 0.6% of the mass. There are also options of combined synthesis of antiknock gasoline and diesel fuel (table 1, options 1^d and 2^e).

Development of the feasibility study for the specific technology option with consideration of material and thermal expenses and consumption indicators for both major and supplemental materials will be provided within the contract.

Diagram 1. Scheme of the block of industrial unit for production of antiknock gasoline from natural gas

Table 2. List of the key technological equipment for the industrial unit for production of diesel fuels from synthetic gas

№	Name of the apparatus	Material for the apparatus
1	Reactors	12Х18Н10Т
2	Gas heating stove	Pipe coil - 15Х5М
3	Heat exchanger-recuperator	12Х18Н10Т
4	Dust filter	12Х18Н10Т
5	Synthetic gas compressor
6	Circulation compressor
7	High pressure separator	12Х18Н10Т
8	Three-phase separator	12Х18Н10Т
9	Refrigerator-condenser	12Х18Н10Т
10	Gas processing tower	ВСт3сп
11	Heat exchangers	12Х18Н10Т, ВСт3сп
12	Containers for collecting liquid products	12Х18Н10Т, ВСт3сп
13	Pumps for liquid products

1. Total weight of technological equipment for the "turn key" block of gasoline synthesis is roughly 2.500 tons.

2. The site area for installation of technological equipment of the block of gasoline synthesis without commodity park and gas turbine generator is about 100X200 m (minimal).

Table 3. Impact of the length of bi-functional catalyst run-on operation on the key readings of hydrocarbon production process from synthetic gas (mixture of СО, СО₂ and Н₂) in isothermic reactor (pilot testing data).

Length of catalyst run-on operation, h	10	60	110	380	460	470
Temperature, оС	400	400	400	400	420	400
Conversion, %:
СО	97	89	95	91	93	86
H2	95	94	94	96	95	96
CO2	94	88	88	90	88	87
Composition of reaction products, % of the mass:
Hydrocarbons	37,8	35,7	37,2	36,2	38,0	38,0
H20	60,0	60,9	59,7	60,1	59,7	57,5
СН3ОН+(СН3)2О	2,2	3,4	3,1	3,7	2,3	4,5
Composition of gasoline cut, % of the mass:
C3+C4	4,7	6,2	5,2	7,2	10,8	9,4
n-С5+	5,4	6,0	5,8	2,7	3,4	3,0
iso-С5+	53,4	54,1	62,1	66,0	56,9	56,6
Napthenes+olefins	8,6	7,3	5,3	4,1	6,8	5,6
Aromatic hydrocarbons, including:	27,9	26,4	21,6	20,0	22,1	25,4
Benzene	0,3	0,3	0,4	0,4	0,4	0,3
Methyl benzene	1,2	1,0	0,8	0,8	0,7	0,8
Dimethylbenzene	16,4	12,8	10,6	9,4	10,0	11,5
С9+	10,0	12,3	9,8	9,4	11,0	12,8
Output of gasoline cut per supplied synthetic gas, g/nm3	153	143	135	130	135	130

Table 4. Consumption data on the feedstock, byproducts, electric power, key and additional materials of the gasoline synthesis block.

№	Material and energy	Consumption per 1 ton of commercial gasoline*
1.	Synthetic gas feedstock after purification and compression (block inlet)	7500-8100 nm3
2.	Hydrocarbon gases (sum of blow down and tank stabilization gas) (in the outlet)	600-1200 nm3 (supplied to gas turbine plant for production of electric power)
3.	Commercial propane-butane cut	to 0,05-0,1 t
4.	Commercial carbonic acid ("dry ice")	to 0,25 t
5.	Supply of water for water rotation cycle	Less than 1 ton (i.e. is fully covered by water formed during gasoline synthesis)
6.	Electric power	200 KWh
7.	Electric power generated by the gas turbine plant (hydrocarbon combustion heat energy is equivalent to 19-20 МJ/nm3 or 5,3-5,6 KWh/nm3)	From 1000 KWh (efficiency coefficient = 0,3; 600 nm3hydrocarbon gases) to 3600 KWh (efficiency coefficient = 0,55; 1200 nm3 hydrocarbon gases)

*Consumption data are given within the range depending on the ratio of active components (Н₂, СО и СО₂) and content of inert gases (N₂, СН₄) in the synthetic gas feedstock, liquefied gas extraction level (propane- butane cut) and etc.