Synthetic petroleum, method of its production, catalyst for this method and method to produce catalyst

FIELD: petroleum chemistry.

SUBSTANCE: invention relates to petroleum chemistry, gas chemistry, coal chemistry. It refers to synthetic petroleum, that features the following content of the components: content of alkanes - at least 80 W%, C5-C10 fractions- at least 50 W%, content of aromatic compounds - not over 0.5 W%.The catalyst to produce synthetic petroleum was also applied for containing a carrier and an active component. Zeolite HBETA is used as a catalyst containing 1-2 W% of extralattice aluminium while the active component is represented by cobalt with the content of 10-60 W% of the catalyst weight The invention refers also to the method of catalyst production, and to that of synthetic petroleum production.

EFFECT: invention relates to petroleum chemistry, gas chemistry, coal chemistry.

8 cl, 7 ex, 1 tbl

 

The technical field to which the invention relates.

The invention relates to petrochemistry, gas chemistry, coal chemistry and relates to synthetic oil, how you can get it from synthesis gas, the catalyst for its preparation and method of producing the specified catalyst.

The level of technology

Currently one of the main methods of production of synthetic motor fuels technology is a "Gas to liquid" ("GTL"). Modern GTL process in its hydrocarbon variant three-stage technology that uses a catalytic reaction. First, methane, constituting the major part of natural and associated gas into reactive mixture of carbon monoxide and hydrogen (synthesis gas). For this purpose, are used in the main steam or autothermal reforming, less partial oxidation. The second stage is the synthesis of hydrocarbons from CO and H2("Fischer-Tropsch synthesis"). At the third stage of hydrocarbon products bring to product quality, using the hydrocracking or hydroisomerization.

The preparation of hydrocarbons from synthesis gas (Fischer-Tropsch synthesis") is a key stage in the GTL process, because it determines the yield and composition of products. In this method it is possible to synthesize the following products, traditionally derived from petroleum:

- low molecular weight olefins (C2-C4);

petrol (C5-the 10);

- diesel fuel (C11-C18);

- paraffin wax (C19+) - ceresin;

- aromatic hydrocarbons;

- a mixture of liquid hydrocarbons and synthetic oil.

Obtaining one or another of a number of products depends on the process conditions and the used catalyst. At the present time almost universally preferred cobalt systems, because they are more selective in respect to the education of linear paraffins. In their presence produces only small amounts of olefins and oxygen-containing compounds. The products of synthesis are not Chiclana and aromatic hydrocarbons.

Of particular interest With bifunctional catalysts based on zeolites, combining properties of the catalyst in the Fischer-Tropsch synthesis and zeolites (patent GB 2211201 And international application WO 01/85650 A1, WO 01/26810 A1). Their application in the synthesis can afford to get synthetic oil at one stage. In the literature, yet it is proposed to produce synthetic crude oil processing biomass, hydroponically crude oil or coking coal (for example, patents GB 2237815 And US 6016868, US 4273643). However, it differs in composition, presence of sulphur-, nitrogen and aromatic compounds.

Known synthetic oil obtained by processing biomass, Patan is the GB 2237815 And, characterized by the following contents of hydrocarbons: With5-C17- 60-80%, the rest is a hydrocarbon, C18+. In addition to the hydrocarbons in the reaction products may contain Cox, gray - and nitrogen-containing compounds.

The main disadvantages of synthetic oil in patent GB 2237815 And are content in her gray - and nitrogen-containing compounds.

Known catalyst for the synthesis of synthetic oil in patent GB 2237815 A. the Catalyst contains either pure aluminum oxide, or a mixture of aluminum oxide with the addition of a crystalline aluminosilicate zeolite, silica gel, sodium oxide and oxides of rare earth elements.

The main disadvantages of this catalyst according to the patent GB 2237815 And are not sufficiently high activity and selectivity of the proposed catalytic system. The yield of liquid hydrocarbons is about 60-70 wt.%, and in some cases just 36-52 wt.%.

A known method of producing a catalyst for production of synthetic oil in patent GB 2237815 A. the Catalyst was prepared by mechanical mixing of alumina or a crystalline aluminosilicate zeolite or silica gel or sodium oxide and oxides of rare earth elements.

The main disadvantages of the method of preparation of the catalyst according to the patent GB 2237815 And are not sufficiently high activity and electively the resulting catalytic system. The catalyst obtained by the proposed method allows to obtain synthetic oil, similar in composition to get us, but containing gray - and nitrogen-containing compounds.

A known method of production of synthetic oil from biomass by patent GB 2237815 a Method of obtaining includes the catalytic cracking of biomass consisting of vegetable oils and/or animal fat, and/or rubber, at a pressure of 1-10 atmospheres and temperatures 420-550°C. the Process is carried out using a catalyst containing either pure aluminum oxide, or with the addition of a crystalline aluminosilicate zeolite, silica gel, sodium oxide and oxides of rare earth elements. The catalyst was prepared by mechanical mixing of alumina or a crystalline aluminosilicate zeolite or silica gel or sodium oxide and oxide of rare earth elements.

The main disadvantages of the method of production of synthetic oil in patent GB 2237815 And are high temperature process, and the presence in the reaction products of gray - and nitrogen-containing compounds, which requires additional cleaning this synthetic oil for future use as a commercial product.

Disclosure of inventions

The problem solved by the claimed inventions is to get synthetic oil, th is ne for injection and transport in pipelines in conjunction with crude oil, as well as having improved processing characteristics for further processing. Recently, the most pressing issue is the reduction in oil sulphur-, nitrogen and aromatic compounds, as stricter requirements to oil and commodity products for these connections.

Unified technical result, which is realized with the implementation of the claimed inventions is to improve the composition of the synthetic oil for the exclusion of her gray - and nitrogen-containing compounds with reduced aromatic content.

The technical result is achieved by the fact that synthetic oil includes alkanes With5-C18including alkanes fraction C5-C10and aromatic compounds at the following content, wt.%:

alkanes With5-C18- not less than 80,

including alkanes fraction C5-C10- not less than 50,

aromatic compounds is not more than 0.5.

The technical result is also achieved by the fact that the catalyst of synthetic oil contains a carrier and an active component, as the carrier is zeolite H-Beta containing 1-2 wt.% so the extra-lattice aluminium, and as the active component is cobalt, the content of which is 10-60 wt.% (from the mass of catalyst). Used zeolite H-Beta is characterized by a molar with what compared SiO 2:Al2O3from 18:1 to 150:1. The content in the source media, so the extra-lattice aluminium (1-2 wt.%) was determined by atomic adsorption spectroscopy, x-ray phase analysis (XRD) and infrared spectroscopy (IRS).

This catalyst has a high activity and selectivity for the formation of the target product is a synthetic oil and allows you to get synthetic oil improved composition due to the low content of aromatic compounds and absence in her gray - and nitrogen-containing compounds.

In the particular case of carrying out the invention additionally carry out impregnation of the catalyst at an intermediate stage of its receipt by the solutions of salts of the promoter. The promoters used metals VII-VIII groups of the Periodic table of Mendeleev.

Technical result is achieved in that the catalyst is prepared in the following way: the media, which is used as the zeolite H-Beta containing 1-2 wt.% so the extra-lattice aluminium calcined for 1-24 hours at a temperature of 250-1000°With, put on him the cobalt impregnation with a solution of cobalt salts in two or more stages and subjected to heat processing.

Heat treatment may be carried out by drying and/or calcination.

In the particular case of the catalyst optionally in the W ill result promoters by impregnation of the support with a solution of their salts.

As promoters can be used metals VII-VIII groups of the Periodic table of Mendeleev.

The technical result is also achieved by the fact that synthetic oil get claimed in the invention method, namely the catalytic conversion of CO and H2at the same time as the catalyst used is specified in the invention catalyst.

The implementation of the invention

To obtain synthetic oil by catalytic conversion of synthesis gas is used a catalyst containing a carrier and an active component, as the carrier is zeolite H-Beta containing 1-2 wt.% so the extra-lattice aluminium, and as the active component is cobalt, the content of which is 10-60 wt.% (from the mass of catalyst). Used zeolite H-Beta is characterized by a molar ratio of SiO2:Al2O3from 18:1 to 150:1.

A method of producing a catalyst for synthetic oil, proposed in the present invention, is as follows.

At the first stage of preparation of the catalyst carrier zeolite H-Beta containing 1-2 wt.% so the extra-lattice aluminium calcined within 1-24 hours (preferably 3-8 h) at a temperature of 250-1000°With (preferably 600-700°). Active component (cobalt) is applied in the amount of 10-60 wt.% (from the mass of catalyst), preferably 20-40 wt.%) impregnation of nositelal several stages from a solution of salts of cobalt nitrate, acetate, formate, acetylacetonate, etc.). At each stage, the sample is dried on a water bath and dried and/or calcined in a stream of air at a temperature of from 100 to 1000°With (preferably 200-400° (C) for 0.5-10 hours, preferably 1-5 hours).

In the particular case after one stage of impregnation of the carrier salt of cobalt and subsequent heat treatment additionally carry out impregnation with a solution of salts of the promoters, then again carry out subsequent thermal processing.

Before conducting the synthesis of synthetic oil, the catalyst was activated by reduction in hydrogen flow at a temperature of 300-600°With (preferably 350-500° (C) for 0.5 to 5 hours (preferably 0.5 to 2.5 hours).

Next, the synthesis of synthetic oil from CO and H2carried out in a tubular reactor with a stationary layer corresponding to the invention of the catalyst at a pressure of 10-50 ATM (preferably 15-25 ATM) and a temperature of 150-300°With (preferably 170-250°). The molar ratio of CO:H2in the synthesis gas is 1:1÷3 (preferably 1:2).

Corresponding to the invention is a method of obtaining synthetic oil is characterized by the fact that the obtained synthetic oil does not contain sulphur-, nitrogen-containing compounds and is characterized by a low content of aromatic compounds.

Example 1.

An example of illustrious is getting synthetic oil using a catalyst based on granulated zeolite H-Beta, containing 1-2 wt.% so the extra-lattice aluminium and the ratio of SiO2/Al2O3which equals 18. The granule size of the carrier is 2-4 mm Sample of catalyst comprising 20%Co/H-Beta is prepared in three stages as follows.

1 stage. The specified zeolite H-Beta annealed at 650°C for 6 hours

stage 2. 12.3 g of cobalt nitrate dissolved in distilled water and added to 20 g of the material obtained in stage 1. The mixture is placed in a porcelain Cup and dried on a water bath for 20-40 minutes, and then calcined at a temperature of 250°C for 1 h

3 stage. 12.3 g of cobalt nitrate dissolved in distilled water and added to the material obtained in stage 2. The mixture is placed in a porcelain Cup and dried on a water bath for 20-40 minutes, and then calcined at a temperature of 250°C for 1 h

Before synthesis, the sample of catalyst was activated in a stream of hydrogen at 400°C for 1 h Synthesis of hydrocarbons is carried out in a tubular reactor with a fixed bed of catalyst at P=20 ATM in the temperature range 160-250°using synthesis gas composition WITH/N2=1/2 (mol.).

Examples 2 and 3.

The method of production of synthetic crude oil using the catalyst carried out according to Example 1 except that the first stage is used containing 1-2 wt.% waraseoni what about the aluminum zeolite H-Beta ratio SiO 2/Al2O325 and 38, respectively.

Example 4, 5, 6.

The method of production of synthetic crude oil using the catalyst carried out according to Examples 1-3 except that the zeolite H-Beta ratio SiO2/Al2O318, 25 and 38 used in the powdered state with a fraction size of 0.1-0.25 mm

Example 7.

The method of production of synthetic crude oil using a catalyst based on granulated containing 1-2 wt.% so the extra-lattice aluminium zeolite H-Beta ratio SiO2/Al2O338, promoted to 0.1%Re. A sample of catalyst comprising 20%Co-0.1%of Re/H-Beta is prepared in four steps as follows.

1 stage. The specified zeolite H-Beta annealed at 650°C for 6 hours

stage 2. 12.3 g of cobalt nitrate dissolved in distilled water and added to 20 g of the material obtained in stage 1. The mixture is placed in a porcelain Cup and dried on a water bath for 20-40 minutes, and then calcined at a temperature of 250°C for 1 h

3 stage. 0,0288 g perrhenate ammonium dissolved in distilled water and added to 20 g of the material obtained in stage 2. The mixture is placed in a porcelain Cup and dried on a water bath for 20-40 minutes, and then calcined at a temperature of 450°C for 1 h

stage 4. 12.3 g of cobalt nitrate dissolved in distilled water and DOB is given to material obtained in stage 2. The mixture is placed in a porcelain Cup and dried on a water bath for 20-40 minutes, and then calcined at a temperature of 250°C for 1 h

Recovery and testing of a sample of the catalyst is carried out in accordance with the procedure outlined in Example 1.

Example 8.

The method of production of synthetic crude oil using the catalyst described in Example 7, except that instead of Re apply EN. Activation and conditions of the synthesis is carried out in accordance with the procedure outlined in Example 1.

The test results of samples of the catalysts prepared and tested in accordance with Examples 1-8 shown in the Table below.

Table
The indicators of the process of production of synthetic oil from CO and H2conducted using samples corresponding to the invention
Example[Alwares.], wt.%Conversion, %Selectivity for hydrocarbons5+, %The output of alkanes, wt.%Fractional composition of alkanes, wt.%
With5-C10C11-C18With19+
1 2,090678068302
21,792658070282
31,279688770291
42,080758264333
51,779758560346
61,286688255387
71,091648572262
81,089678270282

Thus, the resulting synthetic oil in the presence of the proposed catalytic systems, has an improved structure in contrast to crude oil, as it doesn't contain sulphur-, nitrogen-containing compounds, characterized by a low content of aromatic compounds. Get synthetic oil contain what it alkanes - not less than 80 wt.%, including alkanes fraction5-C10- not less than 50 wt.%, and can be used as a separate product in the petrochemical industry. It should be noted that the process is characterized by a high degree of transformation of CO - 80-90%.

1. Synthetic oil, including alkanes, including alkanes fraction5-C10and aromatic compounds at the following content, wt.%: alkanes With5-C18not less than 80, including alkanes fraction C5-C10not less than 50, aromatic compounds is not more than 0.5.

2. Catalyst synthesis synthetic oil according to claim 1, characterized in that it contains a carrier and an active component, at the same time as the media used zeolite H-Beta containing 1-2 wt.% so the extra-lattice aluminium, and as the active component is cobalt, the content of which is 10-60 wt.% by weight of the catalyst.

3. The catalyst according to claim 2, characterized in that it further comprises the promoters, which are used metals VII-VIII groups of the Periodic table of Mendeleev.

4. A method of producing a catalyst for the synthesis of synthetic oil according to claim 1, characterized in that the carrier, which is used as the zeolite H-Beta containing 1-2 wt.% so the extra-lattice aluminium calcined for 1-24 hours at a temperature of 250-1000°With, put on him the cobalt impregnation of rest the rum cobalt salts in two or more stages and subjected to heat processing.

5. The method according to claim 4, characterized in that thermal treatment is carried out by drying and/or calcination.

6. The method according to claim 4, characterized in that impose additional promoters by impregnation of the support with a solution of their salts.

7. The method according to claim 6, characterized in that as promoters use metals VII-VIII groups of the Periodic table of Mendeleev.

8. The method of production of synthetic oil, characterized in that carry out the catalytic conversion of CO and H2and as catalyst using the catalyst according to claim 2 or 3.



 

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