Method of determining polymerizing activity of unsaturated compound hydrogenation catalysts

FIELD: petrochemical process catalysts.

SUBSTANCE: invention relates to determining polymerizing activity of catalysts that can be used for hydrogenation of unsaturated compounds contained in liquid pyrolysis products. As a variable reflecting polymerizing activity of hydrogenation catalysts, optical density value of liquid mixture is used, said mixture containing unsaturated compounds and being kept in contact with catalyst at elevated temperature for a predetermined period of time. Determination of polymerizing activity is accomplished by comparing optical density of liquid mixture containing unsaturated compounds before and after its contact with catalyst. In order to measure optical density of liquid mixture, standard laboratory equipment (photocolorimeter and spectrophotometer) may be utilized.

EFFECT: enabled comparison of polymerizing activity of catalysts directly with respect to industrial feedstock.

3 cl, 2 dwg, 3 tbl, 38 ex

 

The invention relates to the petrochemical industry, specifically to a method of determining polimerizuet activity of catalysts that can be used for hydrogenation of unsaturated hydrocarbons contained in the composition of the liquid products of pyrolysis.

For obtaining aromatic hydrocarbons from liquid products of catalytic reforming or pyrolysis necessary preliminary cleaning these products from olefin hydrocarbons. One method of cleaning is catalytic hydrogenation at elevated temperature and pressure.

As catalysts for hydrogenation using catalysts based on metallic palladium, Nickel metal-oxide alumonickelsilicate and aluminoborosilicate contacts (Berens ROAD and other Processing of liquid products of pyrolysis. - M.: Chemistry, 1985, pp.61-108), and catalysts based on platinum metal (A.S. USSR 200096, A.S. USSR 1513014, RF patent 2117029, RF patent 2118981).

A common disadvantage of the known hydrogenation catalysts is the necessity of using in their use of elevated temperatures, which reduces the activity of the catalyst over time, in particular, due to the increased colabrative (Berens ROAD and other Processing of liquid products of pyrolysis. - M.: Chemistry, 1985, p.75-76, 86-87,90-91).

To reduce Smolov the education use a variety of techniques, for example, recycling the hydrogenated feed is cut (the dilution of the raw products of hydrogenation), additive to the raw material polymerization inhibitors, as well as the introduction of the catalyst additives reducing its acidity, for example, compounds of alkali and alkaline earth metals (Berens ROAD and other Processing of liquid products of pyrolysis. - M.: Chemistry, 1985, p.76; Lipovich V.G. and other Effect of alkaline additives on the catalytic properties of aluminoborosilicate catalyst, oil Refining and petrochemistry", No. 3, 1979, page 11-13).

There is no doubt that using the method of pre-assessment polimerizuet the activity of the catalyst for the specific commodity, it is possible, without conducting time-consuming experiments should evaluate the possibility of using a specific catalyst in this system, and also to carry out qualitative and quantitative selection of additives to reduce the resin formation in the industrial process. Reducing colabrative, in turn, can increase mainegenealogy mileage catalyst.

The known method contingent valuation inclination motor fuel to resin formation (GOST 8489-85 "Fuel motor. The method of determining the actual resin (Budarova)"), which consists in evaporation of the test fuel under running water vapor at elevated temperatures (180-225°).

Significant the initial disadvantage of this method - the duration of the test component, taking into account preparation for testing, at least 3 hours. In addition, to perform tests require specialized equipment designed solely for the implementation of this method (unit-type SETTLEMENT), available in every chemical laboratory.

Closest to the claimed technical solution on the totality of symptoms is the way to determine polimerizuet activity of catalysts for hydrogenation of unsaturated hydrocarbons contained in the United Kingdom patent (patent GB 1071253). The value polimerizuet activity (index polimerizuet activity) is determined by the number of model compounds (isoprene), entering into the presence of a catalyst in the polymerization reaction for a given time at a given temperature.

As the initial mixture used solution of isoprene in benzene (8-10 wt.% isoprene), temperature tests ˜177°C (350°F), the exposure time is 60 minutes. The number of isoprene, which entered into reaction, is defined as the difference in the concentration of isoprene in the initial and final solution, the concentration of isoprene in the solution is determined by gas chromatography.

This method of measurement polimerizuet catalytic activity has the following disadvantages:

1. How ru is et to compare the catalysts among themselves, but you can't compare polymerized activity of the same catalyst in relation to various kinds of industrial raw materials containing various unsaturated compounds.

2. Chromatographic method of analysis does not allow you to lock formed in the reaction is practically non-volatile, high molecular weight (resin) connection; in addition, such connections getting in a chromatographic column, worsen its separation capacity that may distort the analysis results.

3. As model substances used low-boiling the diene is isoprene, which may lead to an overestimation of the values polimerizuet activity due to partial evaporation of isoprene in the selection of samples for analysis.

4. High temperature testing - 170°C.

The aim of the present invention is to develop a method for determining polimerizuet activity of catalysts for hydrogenation of unsaturated compounds, allowing to compare polymerized catalytic activity directly in relation to industrial raw materials.

The solution of this problem is achieved by using as values that reflect polymerized activity of the hydrogenation catalyst, the values of optical density of liquid mixtures containing unsaturated compound and seasoned in contact with kata is Isadora hydrogenation over a certain period of time at elevated temperatures. To measure the optical density of the liquid mixture can be used with standard laboratory equipment - photocolorimeter or spectrophotometer, available in almost every chemical laboratory.

As the liquid mixture can be used in real industrial raw materials or a binary mixture of unsaturated hydrocarbons (diene or monoolefins) and an inert solvent, for example high-boiling aliphatic hydrocarbon.

The temperature at which the contact of the catalyst with the liquid phase, is 70-150°C, contact time 10-60 minutes

The method is illustrated by the following examples:

Example 1. In a thick-walled ampoule, stainless steel, displacement ˜10 ml fill in 5 ml of liquid mixtures containing unsaturated hydrocarbons. As the liquid mixture using lightweight fraction pyrolysis tar (the LFP Federation), secreted products from pyrolysis of gaseous raw materials, characterized by intervals boil 30÷110°containing 66,54 wt.% benzene with iodine number (130±2)g J2/100 g and the value of optical density of 0.02.

The ampoule is sealed and kept in a liquid thermostat at a temperature of 135°C for 30 minutes, after which the capsule is unloaded from thermostat, cool the water to room temperature and out of selected fluid sample for the measurement of optical density.

The value of optical density "And" determined on the photocolorimeter ck-2 in the visible region of the spectrum with the optical filter 400 nm, solution, comparison - water; cuvette thickness of 0.5 see if the value of the optical density of the sample is greater than the value of 0.8, produce dilution of the sample with ethyl acetate (ethyl ester of acetic acid) and the absorbance value for the diluted sample is recalculated taking into account the dilution by the formula:

A=aISM(V1/V2),

where aISM- the measured value of the optical density of the diluted sample;

V1- the volume of solvent;

V2- volume liquid samples collected from the vials for analysis.

The resulting value of optical density is of 0.07 (table 1).

Example 2. Aluminumalloy the catalyst for hydrogenation of unsaturated hydrocarbons brand TH-U in the amount of 1.0 g dried for 60 minutes in air at a temperature of 300°C, then placed in a thick-walled ampoule, stainless steel volume ˜10 ml, which is bathed in 5 ml of liquid mixtures containing unsaturated hydrocarbons. As the liquid mixture using lightweight fraction pyrolysis tar (the LFP Federation), secreted products from pyrolysis of gaseous raw materials, characterized by intervals boil 30÷110°containing 66,54 wt.% benzene with iodine number (130±2)g J2

The ampoule is sealed and kept in a liquid thermostat at a temperature of 135°C for 30 minutes, after which the capsule is unloaded from thermostat, cool the water to room temperature and out of selected fluid sample for the measurement of optical density.

The value of optical density for catalyst TH-U is 6.4 (table 1).

Example 3. Measurement polimerizuet activity is conducted according to example 2 by changing the temperature of thermostat to 100°C. the Value of optical density is 3.3 (table 1). To confirm the presence of correlation between the measure of the optical density and the amount of high molecular weight reaction products further define the content of non-volatile residue"that directly reflect the content of high molecular weight reaction products (resins). The indicator "non-volatile residue" is defined by the following procedure: a known volume of the liquid phase is poured into a dry, pre-weighed on an analytical balance, a porcelain crucible, after which the crucible can withstand 18-20 hours in air at room temperature and then at 110°C to constant mass.

"Non-volatile residue (X), g/DM3, is calculated by the formula:

where m2- weight of crucible with "non-volatile residue", g;

m1- weight of empty crucible, g;

V - volume of sample taken fordetermination, cm3.

The number of non-volatile residue" as determined by the above method is to 32.7 g/l (figure 1).

Example 4. Measurement polimerizuet activity is conducted according to example 2 by changing the temperature of thermostat to 70°C. the Value of optical density is 2.0 (table 1).

Example 5. Measurement polimerizuet activity is conducted according to example 2 by changing the catalyst to paradisecity the catalyst for hydrogenation of unsaturated hydrocarbons PKN. The value of optical density of 0.33 (table 1).

Example 6. Measurement polimerizuet activity is conducted according to example 5, by changing the temperature of thermostat to 100°C. the Value of optical density is to 0.19 (table 1). Further define the content of non-volatile residue, which is 2.2 g/l (figure 1).

Example 7. Measurement polimerizuet activity is conducted according to example 5, by changing the temperature of thermostat to 70°C. the Value of optical density is 0.13 (table 1).

Example 8. Measurement polimerizuet activity is conducted according to example 2 by changing the catalyst to cement ecumenically catalyst GTT used for post-combustion of the organic impurities. The value of optical density is over 0.80 (table 1).

Example 9. Measurement polimerizuet activity is conducted according to example 8, by changing the temperature of thermostat to 100° C. the Value of optical density is 0.56 (table 1). Further define the content of non-volatile residue, which is 5.0 g/l (figure 1).

Example 10. Measurement polimerizuet activity is conducted according to example 8, by changing the temperature of thermostat to 70°C. the Value of optical density is 0.35 (table 1).

As can be seen from examples 3, 6, 9, the contents of non-volatile residue" is directly proportionate to the measure of the optical density and the amount of high molecular weight reaction products.

Examples 1-10 show that, despite the fact that the absolute value of the optical density (polimerizuet activity) for any of the catalyst increases with increasing temperature, the relative optical density on temperature is almost independent. Namely, by selecting for each temperature for 100% of the optical density obtained for the catalyst of maximum activity (GO-W), relative activity of the catalyst GTT will be 13-18%for catalyst PKN - 5-7% optical density.

Example 11. In a thick-walled ampoule, stainless steel volume ˜10 ml fill in 5 ml of liquid mixtures containing unsaturated hydrocarbons. As the liquid mixture using lightweight fraction pyrolysis tar (the LFP Federation), secreted products from pyrolysis of gaseous raw materials, the nature of soysauce intervals boiling 70-110° With containing of 84.8 wt.% benzene with iodine number (33±2) g J2/100 g and the value of optical density of 0.02.

The ampoule is sealed and kept in a liquid thermostat at a temperature of 135°C for 30 minutes, after which the capsule is unloaded from thermostat, cool the water to room temperature and out of selected fluid sample for the measurement of optical density.

The resulting value of optical density of 0.05 (table 1).

Example 12. Aluminumalloy the catalyst for hydrogenation of unsaturated hydrocarbons brand TH-U in the amount of 1.0 g dried for 60 minutes in air at a temperature of 300°C, then placed in a thick-walled ampoule, stainless steel volume ˜10 ml, which is bathed in 5 ml of liquid mixtures containing unsaturated hydrocarbons. As the liquid mixture using lightweight fraction pyrolysis tar (the LFP Federation), secreted products from pyrolysis of gaseous raw materials, characterized by intervals of boiling 70÷110°containing of 84.8 wt.% benzene with iodine number (33±2) g J2/100 g and the value of optical density of 0.02.

The ampoule is sealed and kept in a liquid thermostat at a temperature of 135°C for 30 minutes, after which the capsule is unloaded from thermostat, cool the water to room temperature and out of the selected sample fluid metering is of optical density.

The resulting value of the optical density of the catalyst TH-U is 5.0 (table 1).

Example 13. Measurement polimerizuet activity is conducted according to example 12, by changing the catalyst to paradisecity the catalyst for hydrogenation of unsaturated hydrocarbons PKN. The value of optical density is 0.3 (table 1).

Example 14. Measurement polimerizuet activity is conducted according to example 12, by changing the catalyst to cement ecumenically catalyst GTT used for post-combustion of the organic impurities, the value of optical density is 0.56 (table 1).

Example 15. In a thick-walled ampoule, stainless steel volume ˜10 ml fill in 5 ml of liquid mixtures containing unsaturated hydrocarbons. As the liquid mixture using lightweight fraction pyrolysis tar (the LFP Federation), gidrostabilizirovannoy in the presence of hydrogen and plagiarising catalyst, characterized by intervals of boiling 70÷110°containing 83,6 wt.% benzene with iodine number (14±2) g J2/100 g and the value of optical density of 0.02.

The ampoule is sealed and kept in a liquid thermostat at a temperature of 135°C for 30 min, after which the capsule is unloaded from thermostat, cool the water to room temperature and out of selected fluid sample for the measurement of optical density.

P is obtained the value of optical density is 0.02 (table 1).

Example 16. Aluminumalloy the catalyst for hydrogenation of unsaturated hydrocarbons brand TH-U in the amount of 1.0 g dried for 60 minutes in air at a temperature of 300°C, then placed in a thick-walled ampoule, stainless steel volume ˜10 ml, which is bathed in 5 ml of liquid mixtures containing unsaturated hydrocarbons. As the liquid mixture using lightweight fraction pyrolysis tar (the LFP Federation) gidrostabilizirovannoy in the presence of hydrogen and plagiarising catalyst, characterized by intervals of boiling 70÷110°containing 83,6 wt.% benzene with iodine number (14±2) g J2/100 g and the value of optical density of 0.02.

The ampoule is sealed and kept in a liquid thermostat at a temperature of 135°C for 30 min, after which the capsule is unloaded from thermostat, cool the water to room temperature and out of selected fluid sample for the measurement of optical density.

The resulting value of the optical density of the catalyst TH-U is 0.1 (table 1).

Example 17. Measurement polimerizuet activity is conducted according to example 16, by changing the catalyst to paradisecity the catalyst for hydrogenation of unsaturated hydrocarbons PKN. The value of optical density is 0.03 (table 1).

Example 18. Measurement polimerizuet activity spend what about the example 16, changing the catalyst to cement ecumenically catalyst GTT used for post-combustion of the organic impurities. The value of optical density is 0.06 (table 1).

Example 19. In a thick-walled ampoule, stainless steel volume ˜10 ml fill in 5 ml of liquid mixtures containing unsaturated hydrocarbons. As a liquid mixture using a 50% solution of piperidine (1.3 pentadiene) in n-decane, characterized by the value of optical density of 0.01. The ampoule is sealed and kept in a liquid thermostat at a temperature of 150°C for 60 min, after which the capsule is unloaded from thermostat, cool the water to room temperature and out of selected fluid sample for the measurement of optical density.

The resulting value of optical density is 0.02 (table 1).

Example 20. Aluminumalloy the catalyst for hydrogenation of unsaturated hydrocarbons brand TH-U in the amount of 1.0 g dried for 60 minutes in air at a temperature of 300°C, then placed in a thick-walled ampoule, stainless steel volume ˜10 ml, which is bathed in 5 ml of liquid mixtures containing unsaturated hydrocarbons. As a liquid mixture using a 50% solution of piperidine (1.3 pentadiene) in n-decane, characterized by the value of optical density of 0.01. The ampoule is sealed and kept in a liquid is Ostrom thermostat at a temperature of 150° C for 60 min, after which the capsule is unloaded from thermostat, cool the water to room temperature and out of selected fluid sample for the measurement of optical density.

The resulting value of optical density is 0.57 (table 1).

Example 21. Measurement polimerizuet activity is conducted according to example 20, by changing the exposure time ampules in thermostat up to 30 minutes, the absorbance Value is 0.43 (table 1).

Example 22. Measurement polimerizuet activity is conducted according to example 20, by changing the exposure time ampules in thermostat to 10 minutes and absorbance Value 0,26 (table 1).

Example 23. Measurement polimerizuet activity is conducted according to example 20, by changing the catalyst to paradisecity the catalyst for hydrogenation of unsaturated hydrocarbons PKN. The value of optical density is 0.09 (table 1).

Example 24. Measurement polimerizuet activity is conducted according to example 23, by changing the exposure time ampules in thermostat up to 30 minutes, the absorbance Value is 0.08 (table 1).

Example 25. Measurement polimerizuet activity is conducted according to example 23, by changing the exposure time ampules in thermostat to 10 minutes the absorbance Value is 0.08 (table 1).

Example 26. Measurement polimerizuet activity is conducted according to example 20, by changing the catalyst to cement aluminum is nickelmania catalyst GTT, used for post-combustion of the organic impurities. The value of optical density is 0.13 (table 1).

Example 27. Measurement polimerizuet activity is conducted according to example 26, by changing the exposure time ampules in thermostat up to 30 minutes, the absorbance Value is 0.11 (table 1).

Example 28. Measurement polimerizuet activity is conducted according to example 26, by changing the exposure time ampules in thermostat to 10 minutes the absorbance Value is 0.10 (table 1).

Example 29. Aluminumalloy the catalyst for hydrogenation of unsaturated hydrocarbons brand TH-U in the amount of 1.0 g dried for 60 minutes in air at a temperature of 300°C, then placed in a thick-walled ampoule, stainless steel volume ˜10 ml, which is bathed in 5 ml of liquid mixtures containing unsaturated hydrocarbons. As a liquid mixture using a 50% solution of piperidine (1.3 pentadiene) in n-decane, characterized by the value of optical density of 0.01. The ampoule is sealed and kept in a liquid thermostat at a temperature of 150°C for 60 min, after which the capsule is unloaded from thermostat, cool the water to room temperature, the liquid phase is separated from the catalyst and transferred to volumetric flask of 50 ml of the Catalyst was further treated with a solvent, which is used as this is levy ether acetic acid, when the boiling temperature of the solvent for 30 minutes. Obtained by treatment of the catalyst solution containing the resin, add in the same volumetric flask, which is filled in the liquid phase of the capsules, after which the amount of solution in a volumetric flask is brought ethyl ester of acetic acid to a volume of 50 ml. Next, measure the optical density of the resulting solution. The corresponding value of optical density is of 6.96 (figure 2).

Example 30. Measurement polimerizuet activity is conducted according to example 29, by changing the catalyst to paradisecity the catalyst for hydrogenation of unsaturated hydrocarbons PKN. The value of optical density is 0,18 (figure 2).

Example 31. Measurement polimerizuet activity is conducted according to example 29, by changing the catalyst to cement ecumenically catalyst GTT used for post-combustion of the organic impurities. The value of optical density is 0.65 (figure 2).

Example 32. Measurement polimerizuet activity is conducted according to example 29, by changing the catalyst to alumnirelations the catalyst for hydrogenation of unsaturated hydrocarbons brand TH-U, optionally containing in its composition alkaline additive is sodium carbonate in the amount of 0.35 wt.% in terms of sodium. The value of optical density is 3.6 (figure 2).

Example 33. In autoclavable 0.8 l load 50 g pre-restored in the presence of hydrogen alumnirelations catalyst for hydrogenation of unsaturated hydrocarbons brand TH-U and 0.6 l light fraction pyrolysis tar (the LFP Federation), secreted products from pyrolysis of gaseous raw materials, characterized by intervals boil 30÷110°containing 66,54 wt.% benzene with iodine number (130±2) g J2/100 g and the value of optical density of 0.02.

Later in the autoclave serves hydrogen in a quantity sufficient to create a pressure of 30 ATM, and taking the temperature to 135°C. After holding at the given pressure and temperature for 90 minutes, the autoclave is cooled rapidly to room temperature. From the autoclave selected liquid sample, which make determination of the iodine number and absorbance values.

The resulting value of iodine number is (115±2) g J2/100 g, the value of optical density of 6.3 (table 2).

Example 34. Conducted according to example 33, changing the catalyst to paradisecity the catalyst for hydrogenation of unsaturated hydrocarbons LTU.

The resulting value of iodine number is (20±2) g J2/100 g, the value of optical density of 0.02 (table 2).

Example 35. Conducted according to example 33, changing the catalyst to cement ecumenically catalyst GTT used for post-combustion of the organic impurities.

The resulting value of iodine number is (27±2) g J2/100 g, the value of optical density of 0.05 (table 2).

Example 36. Previously restored when outstay hydrogen aluminumalloy the catalyst for hydrogenation of unsaturated hydrocarbons brand TH-U in the amount of 80 g load flowing in a vertical tubular reactor. Later in the reactor serves hydrogen in a quantity sufficient to create a pressure of 30 ATM, and then when the temperature in the reactor 23°To submit to the reactor with the volumetric rate of 330 ml/h light fraction pyrolysis tar (the LFP Federation), secreted products from pyrolysis of gaseous raw materials, characterized by intervals boil 30÷110°containing 66,54 wt.% benzene with iodine number (130±2) g J2/100 g and the value of optical density of 0.02.

After 60 minutes the temperature in the reactor was raised to 350°and after 180 minutes select a sample section of hydrogenated feed, which make determination of the iodine number and absorbance values.

The resulting value of iodine number is (70±2) g J2/100 g, the value of optical density of 4.3 (table 3).

Example 37. Previously restored in the presence of hydrogen aluminumalloy the catalyst for hydrogenation of unsaturated hydrocarbons brand TH-U in the amount of 80 g load flowing in a vertical tubular reactor. Later in the reactor serves hydrogen in a quantity sufficient to create a pressure of 30 ATM, and then when the temperature in the reactor 23°To submit to the reactor with the volumetric rate of 330 ml/h light fraction pyrolysis tar (the LFP Federation) gidrostabilizirovannoy in the presence of hydrogen and plagiarising catalysis is the Torah, characterized by intervals of boiling 70÷110°containing 81,2 wt.% benzene with iodine number (68±2) g J2/100 g and the value of optical density of 0.02.

After 60 minutes the temperature in the reactor was raised to 350°and after 180 minutes select a sample section of hydrogenated feed, which make determination of the iodine number and absorbance values.

The resulting value of iodine number is (46±2) g J2/100 g, the value of optical density of 1.3 (table 3).

Example 38. Previously restored in the presence of hydrogen aluminumalloy the catalyst for hydrogenation of unsaturated hydrocarbons brand TH-U in the amount of 80 g load flowing in a vertical tubular reactor. Later in the reactor serves hydrogen in a quantity sufficient to create a pressure of 30 ATM, and then when the temperature in the reactor 23°To submit to the reactor with the volumetric rate of 330 ml/h light fraction pyrolysis tar (the LFP Federation), gidrostabilizirovannoy in the presence of hydrogen and plagiarising catalyst, characterized by intervals of boiling 70÷110°containing 83,6 wt.% benzene with iodine number (14±2) g J2/100 g and the value of optical density of 0.02.

After 60 minutes the temperature in the reactor was raised to 350°and after 180 minutes select a sample section of hydrogenated feed, for which the Oh make determination of the iodine number and absorbance values.

The resulting value of iodine number is (8±2) g J2/100 g, the value of optical density of 0.07 (table 3).

Table 1.
The optical density of the liquid phase for different catalysts, depending on the composition of the liquid phase, the temperature and time
ExampleThe liquid mixtureCatalystTemperature,°Time, minutesAnd
1The LFP Federation,

(130±2)g J2/100 g; A=0,02
without catalyst135300,07
2TH-86135306,4
3TH-86100303,3
4TH-8670302,0
5PKN135300,33
6PKN100300,19
7PKN70300,13
8GTT135300,80
9The TT 100300,56
10GTT70300,35
11The LFP Federation,

(33±2) g J2/100 g; A=0,02
without catalyst135300,05
12TH-86135305,0
13PKN135300,30
14GTT135300,63
15Gidrostabilizirovannoy the LFP Federation, (14±2) g J2/100 g;

A=0,02
without catalyst135300,02
16TH-86135301,10
17PKN135300,09
18GTT135300,14
1950% solution of piperidine (1.3 pentadiene) in n-decane;

A=0,01
without catalyst150600,02
20TH-86150600,57
21TH-86 150300,43
22TH-86150100,26
23PKN150600,09
24PKN150300,08
25PKN150100,08
26GTT150600,13
27GTT150300,11
28GTT150100,10

Table 2.
The optical density and the iodine number of the liquid phase for different catalysts (experiments in the presence of hydrogen in the autoclave)
ExampleThe liquid mixtureCatalystTemperature, °Pressure, ATM.Time,

minutes
Iodine numberAnd
33The LFP Federation,

(130±2) g

J2/100 g;

A=0,02
TH-86 1353090115±26,3
34PKN20±20,02
35GTT27±20,05
Table 3.
The optical density and the iodine number of the liquid phase for different catalysts (experiments in the presence of hydrogen in a flow reactor)
ExampleThe liquid mixtureCatalystTemperature, °Pressure, ATM.Iodine numberAnd
36The LFP Federation,

(130±2) g J2/100 g; A=0,02
TH-863503070±24,3
37Gidrostabilizirovannoy the LFP Federation (46±2)g J2/100 g;

A=0,02
TH-8646±21,3
38Gidrostabilizirovannoy the LFP Federation (14±2) g Jsub> 2/100 g;

A=0,02
TH-868±20,07

1. The method of determining polimerizuet activity of catalysts for hydrogenation of unsaturated hydrocarbons by comparing the characteristics of liquid mixtures containing unsaturated hydrocarbons, before and after its contact with the catalyst at elevated temperature, characterized in that as the characteristic polimerizuet activity using the optical density of the liquid mixture.

2. The method according to claim 1, characterized in that the contact of the liquid mixture with the catalyst is carried out at a temperature of 70-150°C for 10-60 minutes

3. The method according to claim 1, characterized in that the liquid mixture using a 50%solution of piperidine (1.3 pentadiene) in n-decane.



 

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13 cl, 2 dwg, 1 tbl

FIELD: petroleum processing.

SUBSTANCE: invention, in particular, relates to petroleum fraction hydrofining process utilizing presulfided catalysts. Hydrofining process is described involving contacting petroleum fractions with presulfided catalyst containing alumina-carried cobalt, molybdenum, phosphorus, and boron, said process being conducted at 320-340°C, pressure 3.0-5.0 MPa, volumetric feed supply rate 1.0-6.0 h-1, normalized volumetric hydrogen-containing gas-to-feed ratio (500-1000):1 in presence of catalyst sulfided outside of reactor. Sulfidizing of catalyst is accomplished with hydrogen sulfide at 80-500°C and volumetric hydrogen sulfide flow rate 0.02-6.0 h-1. Chemical composition of catalyst is the following, wt %: MoS2 8.0-17.0, Co3S2 1.5-4.0, P2O3 2.5-5.0, B2O3 0.3-1.0, La2O3 1.0-5.0, and aluminum oxide - the balance.

EFFECT: simplified process.

2 cl, 1 tbl, 3 ex

FIELD: petroleum processing.

SUBSTANCE: two or more types of hydrocarbon stock with sulfur level above 50 ppm are combined to form blended stock. The latter is subjected to hydrodesulfurization step to reduced sulfur resulting in production of reduced-sulfur hydrocarbon fraction. Process is adjusted so that a situation is achieved wherein level of sulfur in hydrocarbon product is close or equal to desired sulfur level, production of hydrocarbon product with desired sulfur level being optimized through integrated control of hydrocarbon stock blending step and installation operation in hydrodesulfurization step taking into account level of sulfur in blended hydrocarbon product subjected to hydrodesulfurization.

EFFECT: maximized production of lower sulfur-level gas oil.

24 cl, 4 cl

FIELD: petroleum processing.

SUBSTANCE: two or more types of hydrocarbon stock with sulfur level above 50 ppm are combined to form blended stock. The latter is subjected to hydrodesulfurization step to reduced sulfur resulting in production of reduced-sulfur hydrocarbon fraction. Process is adjusted so that a situation is achieved wherein level of sulfur in hydrocarbon product is close or equal to desired sulfur level, production of hydrocarbon product with desired sulfur level being optimized through integrated control of hydrocarbon stock blending step and installation operation in hydrodesulfurization step taking into account level of sulfur in blended hydrocarbon product subjected to hydrodesulfurization.

EFFECT: maximized production of lower sulfur-level gas oil.

24 cl, 4 cl

FIELD: petroleum processing.

SUBSTANCE: process consists in interaction of feedstock with hydrogen in presence of hydrofining catalyst under suitable conditions and includes stage wherein catalyst is moistened with water added to feedstock in amounts between 0.01 and 10 vol %.

EFFECT: prolonged service time of hydrofining reactor and increased silicon capacity of hydrofining catalyst.

2 cl, 2 tbl, 2 ex

FIELD: production of catalytic compositions.

SUBSTANCE: proposed method includes combining and bringing into interaction at least one component of non-precious metal of group VII and at least two components of metal of VIB group in presence of proton liquid; then composition thus obtained is separated and is dried; total amount of components of metals of group VIII and group VIB in terms of oxides is at least 50 mass-% of catalytic composition in dry mass. Molar ratio of metals of group VIB to non-precious metals of group VIII ranges from 10:1 to 1:10. Organic oxygen-containing additive is introduced before, during or after combining and bringing components into interaction; this additive contains at least one atom of carbon, one atom of hydrogen and one atom of oxygen in such amount that ratio of total amount of introduced additive to total amount of components of metals of group VIII to group VIB should be no less than 0.01. This method includes also hydraulic treatment of hydrocarbon material in presence of said catalytic composition.

EFFECT: enhanced efficiency.

29 cl, 8 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention provides petroleum fraction hydrofining catalyst with following chemical analysis, wt %: CoO 2.5-4.0, MoO3 8.0-12.0, Na20.01-0.08, La2O3 1.5-4.0, P2O5 2.0-5.0, B2O3 0.5-3.0, Al2O3 - the balance.

EFFECT: enhanced hydrofining efficiency in cases of feedstock containing elevated amount of unsaturated hydrocarbons.

2 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: catalytic system of hydrocarbon feedstock hydrofining is activated by circulating hydrogen-containing gas or mixture thereof with starting feedstock through layer-by-layer loaded catalysts in presulfided or in presulfided and oxide form at elevated temperature and pressure. Hydrogen is injected into circulating hydrogen-containing gas or mixture thereof with starting feedstock portionwise, starting concentration of hydrogen in circulating hydrogen-containing gas not exceeding 50 vol %. Starting feedstock consumption is effected stepwise: from no more than 40% of the working temperature to completely moistening catalytic system and then gradually raising feedstock consumption to working value at a hourly rate of 15-20% of the working value. Simultaneously, process temperature is raised gradually from ambient value to 300-340°C. Circulating factor of hydrogen-containing gas achieves 200-600 nm3/m3. Addition of each portion of hydrogen is performed after concentration of hydrogen in circulating hydrogen-containing gas drops to level of 2-10 vol % and circulation of hydrogen-containing gas through catalysts loaded into reactor begins at ambient temperature and further temperature is stepwise raised. Starting feedstock, which is straight-run gasoline or middle distillate fractions, begins being fed onto catalytic system at 80-120°C.

EFFECT: enabled prevention and/or suppression of overheating in catalyst bed.

5 cl, 6 tbl, 12 ex

FIELD: oil refining and petro-chemistry.

SUBSTANCE: proposed method consists in bringing the raw material containing at least 80 mass-% of normal waxes at solidification point above 60°C in contact with catalyst containing noble metal and amorphous porous alumino-silicate carrier; the process is conducted under hydroisomerizatiion conditions.

EFFECT: improved quality of micro-crystalline wax.

20 cl, 1 tbl, 1 ex

FIELD: petroleum chemistry.

SUBSTANCE: invention relates to microcrystalline paraffin obtained by catalytic hydroisomerization at temperature more than 200°C from FT paraffin having from 20 to 105 carbon atoms. Microcrystalline paraffin is non-liquid at 25°C, but at least pasty with needle penetration less than 100x10-1, measured according to DIN 51579. Disclosed is method for production of microcrystalline paraffin.

EFFECT: microcrystalline paraffin free from naphthenes and aromatics.

17 cl, 1 dwg, 1 tbl, 3 ex

FIELD: petroleum processing.

SUBSTANCE: invention, in particular, relates to petroleum fraction hydrofining process utilizing presulfided catalysts. Hydrofining process is described involving contacting petroleum fractions with presulfided catalyst containing alumina-carried cobalt, molybdenum, phosphorus, and boron, said process being conducted at 320-340°C, pressure 3.0-5.0 MPa, volumetric feed supply rate 1.0-6.0 h-1, normalized volumetric hydrogen-containing gas-to-feed ratio (500-1000):1 in presence of catalyst sulfided outside of reactor. Sulfidizing of catalyst is accomplished with hydrogen sulfide at 80-500°C and volumetric hydrogen sulfide flow rate 0.02-6.0 h-1. Chemical composition of catalyst is the following, wt %: MoS2 8.0-17.0, Co3S2 1.5-4.0, P2O3 2.5-5.0, B2O3 0.3-1.0, La2O3 1.0-5.0, and aluminum oxide - the balance.

EFFECT: simplified process.

2 cl, 1 tbl, 3 ex

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