The method of producing catalyst for the hydrogenation of aromatic hydrocarbons

 

(57) Abstract:

Features a method of producing catalyst for the hydrogenation of aromatic hydrocarbons, including the introduction of the carrier compounds of tungsten and Nickel. Compounds of tungsten and Nickel contribute by one-step impregnation by water absorption of the carrier or from discharge of stable excess of a solution containing both compounds tungsten and Nickel and compounds of tungsten using ammonium tungsten acid or tungstic acid, and the solution is stabilized by the introduction of phosphoric acid, or nitric acid, or hydrogen peroxide, or ammonia, or combinations thereof. The proposed invention allows to simplify the method of producing catalyst not containing precious metals, based on the resource base of the components of fixed quality. 1 C.p. f-crystals, 1 table.

The invention relates to the refining and petrochemical industries, in particular to the field of environmentally clean unleaded gasoline, including by catalytic hydrogenation of aromatic hydrocarbons.

Known methods for producing catalysts for the hydrogenation of aromatic hydrocarbons by drawing on media Utilizatori hydrogenation: USP, 67 (7), 1998, S. 656-687].

These catalysts are expensive, and most importantly, extremely sensitive to poisoning of the catalyst poisons present in the actual raw materials (gasoline, diesel fraction).

A known method of producing catalyst for the hydrogenation of aromatic hydrocarbons by a two-step impregnation specially prepared media Tio2-Al2ABOUT3solutions metavolume ammonium and nitrate Nickel and ruthenium (or palladium) [U.S. patent 5229347, 20.07.1993] with intermediate annealing. The resulting catalyst contained 20% WO3, 6% NiO and 0.6% RUO Li2on the media 66.4% of Tio2+Al2ABOUT3.

The disadvantages of this method is, first, the high price of the obtained catalyst due to the high content of precious metals (Ru, or Pd), and secondly, high energy consumption due to the need for an intermediate high temperature calcination, third, complex technology of preparation of Ti-containing media.

A method of obtaining catalysts for hydrogenation of aromatic hydrocarbons by impregnation of the alumina carrier with an aqueous solution of compounds of tungsten and Nickel intermediate calcining, the tungsten unositsja; has a so-called magginesu structure and specially synthesized with the use of sophisticated techniques (recrystallization, the separation of the cation and others) [RF patent 2050190, Appl. 23.07.93, publ. 20.12.95].

This method, in addition to the aforementioned complexity, also has the following disadvantages: low degree of reproducibility of complex salts of tungsten and, as a consequence, the irreproducibility of the composition and properties of the catalyst, the low degree of thermal stability of the catalyst, determined by the temperature of thermal decomposition of the complex salt of tungsten.

Closest to the proposed technical solution to the technical essence and the achieved effect is a method for the catalytic hydrogenation of hydrocarbons by one-step impregnation ministerialnego carrier with an aqueous solution of ammonium tungsten-acid and Nickel nitrate, stable monoethanolamine, followed by drying and calcining [U.S. patent 3397249, publ. 13.08.1968].

The disadvantage of this method is, first, the impossibility of its use in real industrial production for use as a stabilizer solution combustible substance-monoethanolamine acid).

In addition, a solution of ammonium tungsten-acid and Nickel nitrate, stable monoethanolamine, has a very low concentration WO3and NiO, which does not allow to regulate the content of active components in the catalyst, and consequently, the activity of the catalyst.

The aim of the present invention is to increase activity and simplification of the method of preparation of the catalyst for hydrogenation of aromatic hydrocarbons that do not contain precious metals, as well as the expansion of raw materials of the components of fixed quality.

This objective is achieved in that the preparation method of catalyst for the hydrogenation of aromatic hydrocarbons include one-step impregnation of the carrier by absorption stabilized solution containing both compounds of tungsten and Nickel, or from discharge of excess stable solution, and the solution stabilize the introduction of phosphoric acid, or nitric acid, or hydrogen peroxide, or ammonia, or combination thereof. As compounds of tungsten, preferably using ammonium tungsten acid or tungstic acid.

Preparation of catalyst containing WO3and NiO, put quality, is a technological way to implement it in terms of existing catalyst productions.

In the preparation of stable nikelsoderzhashchih solutions based on ammonium tungsten acid is preferably used as stabilizing compounds phosphoric acid, or nitric acid, or hydrogen peroxide, or a combination thereof, and on the basis of tungstic acid, H2WO4- preferably ammonia.

Introduction WO3and NiO in the carrier by impregnation simultaneously from one solution creates favorable conditions for the formation of the active phase of the catalyst in the oxide close to the connection type NiOWO3. Stabilization of the impregnating solutions the introduction of phosphoric acid, or nitric acid, or ammonia, or combination thereof allows for a wide variety concentration in solution compounds of tungsten and Nickel when their optimal ratio.

Thus, the present invention meets the criteria of "novelty" and "significant difference".

The following are specific examples of implementation of the proposed method.

Example 1. The preparation of the catalyst impregnated in4nH2O

2. Nickel nitrate Ni(NO3)6N2ABOUT

3. Acid tungsten H2WO4< / BR>
4. Tungsten trioxide (WO3< / BR>
5. Orthophosphoric acid, H3Rho485%

6. Acid nitric NGO356%

7. The hydrogen peroxide H2ABOUT230%

8. Ammonia water 25%

9. Water

10. Medium alumina extrudates, -Al2ABOUT3< / BR>
The preparation of the impregnating solution.

100 ml of water heated to 60oWith sleep 60 g of ammonium tungsten acid and 50oWith stirred for 1 h Salt is fully dissolved. Enter in a solution of 40 ml of 30% hydrogen peroxide solution, stirred for 0.5 H. the solubility of salt is increased, however, complete dissolution does not. Enter into the solution of 11.4 ml of 85% orthophosphoric acid and at 50-60oWith stirred for 15 min to obtain the true solution. Then the solution portions contribute 59 g of Nickel nitrate and 40-50oWith stirred for 0.5 h, get 210 ml of true dark green solution with a pH of 1.4. The solution is cooled and incubated for 15 h at room temperature. Sludge is not observed, the solution is transparent.

The carrier impregnated.

300 g but eshivot for 0.5 h until complete absorption of the solution.

The heat treatment of the impregnated carrier.

The impregnated carrier is dried at 120oC for 4 h, and calcined at 500oC for 10 h

The catalyst composition, wt.%: WO3- 13,95; NiO - 3,8; P2O5- 4,1; Al2O3- the rest.

The strength of the catalyst 2.0 kg/mm of diameter.

Example 2. Testing of the catalyst on the activity.

Raw materials - benzene.

Installation micropolicy.

Catalyst loading of 10 cm3.

The test procedure:

Drying of the catalyst in a stream of hydrogen at a gradual rise up to 120oC, holding at 120oC for 1 h

The rise of temperature from 120 to 420oWith speeds of 50oS/h Exposure at 400-420oWith the current hydrogen consumption 300 nm3/m3during the 5 o'clock

Cooling in a stream of hydrogen to 150oC.

Submission of benzene at 150oC and 40 MPa with a bulk velocity 2 h-1. Determination of conversion of benzene chromatographic.

Temperature rise in the catalyst bed to

200oWith the definition of the conversion of benzene

220oWITH- -------- - ---------

240oWITH- -------- - ---------

275oWITH- -------- - ---------

The catalyst of example 1 has activity in the hydrogenation of benzene to 90% at 220oC and 40-50 MPa.

Example 3. The preparation of the catalyst by impregnation of the support in excess of the solution from draining excess solution.

The reagents of example 1.

The preparation of the impregnating solution.

160 ml of water is heated to 60-70oC and under stirring portions enter 80,7 g of ammonium tungsten acid. The incomplete dissolution. Enter 36 ml of 30% hydrogen peroxide solution with stirring for 0.5 h and 5.7 ml of 85% phosphoric acid with stirring for 15 minutes to dissolve the ammonium tungsten acid.

25 ml of water is heated to 55-60oWith and contribute 112 g of Nickel nitrate with stirring for 0.5 h

A solution of Nickel nitrate poured into a solution of ammonium tungsten acid and 55oWith stirred for 0.5 hours Received the true solution is dark green, the volume of 320 ml, pH of 1.3.

The solution has been aged for 14 h, the precipitate no, the solution is transparent.

The carrier impregnated.

300 g of the carrier is dried at 80-100oC for 1 h

Dried carrier at 50-60oWith CLASS="ptx2">

The heat treatment of the impregnated carrier of example 1.

The catalyst composition, wt.%: WO3is 22.6; NiO - 5,0; R2O5- is 3.08; Al2O3- the rest.

The strength of the catalyst according to example 3 splitting 1.9 kg/mm

The activity of the catalyst according to example 3 was 83% at 220oC and 40-50 MPa.

Example 4.

The preparation of the impregnating solution.

The reagents of example 1.

120 ml of water is heated to 60-70oWith injected into the water to 54.5 g of ammonium tungsten acid under stirring for 0.5 h, then enter 12 ml of 30% hydrogen peroxide is stirred for 0.5 h; 54,5 g of Nickel nitrate, 10 ml of water, stirred for 0.5 h; 12 ml of 30% hydrogen peroxide; 8 ml of nitric acid (56%), stirred for 0.5 h and bring the volume of solution by the addition of water up to 210 ml, pH of 1.7.

The carrier impregnated.

300 g of the carrier is dried at 80-100oWith over 1 teaspoon of Dried media pour solution at 50-60oC and stirred until a complete and uniform absorption within 0.5 hours

Thermal treatment of the catalyst of example 1.

The catalyst composition, wt.%: WO3- 13,1; NiO - 4,0; Al2O3- the rest.

Example 5

The preparation of the impregnating solution.

200 ml of ammonia water was heated to 50oWith and enter 48 g of tungstic acid with stirring for 0.5 hours the resulting solution was injected a solution of Nickel nitrate (or 37.4 g of Nickel nitrate + 50 ml water), stirred for 0.5 hours, the Volume of the solution 290 ml, pH 8.5.

The carrier impregnated.

260 g of the carrier is dried at 80-100oWith over 1 teaspoon of Dried media fill an impregnating solution at 50-60oC and stirred for 1.0 h, after which the excess solution is drained (80 ml).

The heat treatment of the impregnated carrier of example 1.

The catalyst composition, wt.%: WO3- 13,4; NiO - 3,3; Al2O3- the rest.

The strength of the catalyst according to example 5 is 1.9 g/mm

The activity of the catalyst according to example 5 was 86,5% at 220oC and 40-50 MPa.

The table presents the synthesis conditions and properties of the catalysts for the proposed method (examples 1, 3 and 5), as well as the conditions outside the claimed range (examples 6, 7) and by the way the prototype (example 8).

As can be seen from the presented data, the samples of the catalysts prepared according psokas mechanical strength (1.9 to 2.1 kg/mm) and activity (86,5-91% conversion of benzene).

Comparison of conditions for the synthesis of catalysts for the proposed method and their quality catalysts, synthesized for the stated limits, shows that the use of as compounds of tungsten tungsten trioxide and sulfuric acid as a stabilizer solution does not allow to realize the inventive method, since the solution is either unstable or stabilized at a very high dilution. In the first case (example 6) active ingredients for the most part deposited on the surface of the granules of the media and after the heat treatment showered in the form of dust; the obtained catalyst has a low content of active components and as a consequence, the low activity. In the second case (example 7) in the catalyst cannot enter the active ingredients in the required amount due to the low concentration of the impregnating solution, whereupon the catalyst is practically inactive.

The desire to enter the active components in examples 6-7 more by increasing time to treatment (10-12 h) led to a sharp decrease in strength of the catalyst (1.2 to 1.3 kg/mm against the 1.9-2.1 kg/mm) compared with the catalyst according to the claimed method.

Comparison of catalysts for saulk as the introduction of active ingredients is carried out from solutions stable non-flammable organic acids and basis, the concentration of the stable impregnating solution is adjusted within a wide range that allows you to enter the active ingredients in the required amount, the time of interaction of the carrier with a solution of 0.5 to 1.0 h vs. 20-30 hours To the same long-term ageing of the carrier in the solution by the method prototype leads to a sharp decrease in strength of the catalyst effect risparmi") from 1.9-2.1 kg/mm to 0.9.

The inventive method allows you to use as wolframtones compounds as ammonium tungsten acid, and tungstic acid, which expands the resource base catalyst.

Thus, the described method compared with the method of the prototype allows to obtain a set of catalysts with high catalytic activity in the hydrogenation of aromatic compounds and high mechanical strength.

The method of producing catalyst for the hydrogenation of aromatic hydrocarbons by one-step impregnation of the carrier by water absorption stabilized solution containing both compounds of tungsten and Nickel, or from discharge of excess stable solution, different those who ammonia, or a combination thereof.

2. The method according to p. 1, characterized in that compounds of tungsten using ammonium tungsten acid or tungstic acid.

 

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