DE3013154C2 - Catalyst for the hydrogenation treatment of hydrocarbons, process for its production and its use - Google Patents

Description

2. A method for producing the catalyst according to claim 1 by impregnating an optionally containing S1O2 support made of aluminum oxide or alumina with a stabilized nickel, Molybdenum and phosphorus-containing solution, subsequent drying and calcining, characterized in that the impregnated carrier is shaped and, after calcining, is again impregnated, dried and calcined, with a solution in at least one of the impregnation stages is impregnated, which contains compounds of nickel and molybdenum as well as phosphoric acid and in the d.3 molybdenum to nickel molar ratio approx 3: 1 and the molar ratio of phosphorus to molybdenum does not exceed 0.087.

3. Use of the catalyst according to claim 1 for the hydrogenation treatment of hydrocarbons to remove sulfur, nitrogen and / or metals.

The invention relates to an improved catalyst made of MoO ^ NiO / PjOs support, which is suitable for the hydrogenation treatment of hydrocarbons. on a process for the preparation of the catalyst and on its use for hydrogenating Treatment of hydrocarbons.

Hydrogenation treatment refers to the process of hydrogenating desulphurization, denitrogenation and demetallation of hydrocarbon feeds. The invention is particularly directed to the preparation of a catalyst having superior activity the hydrogenation treatment with removal of sulfur and nitrogen contents from high boiling points Hydrocarbon materials directed. Examples of such high boiling point materials are complete Crude oil. Crude distillate residues, atmospheric and vacuum gas oils and cycle oils c.

Crude oil and high-boiling hydrocarbon fractions and / or distillates from the raw materials contain components such as nitrogen, sulfur and metal contents. These impurities can exist in heteroatonn-n of compounds and are often present in relatively large quantities. Such impurities can lead to processing treatment of petroleum fractions in reforming or cracking steps poison or change. Nitrogen and sulfur are also troublesome because of the burning of hydrocarbon fuels that contain these contaminants. Releases nitrogen and sulfur oxides. Such gases as by-products are poisonous, corrosive and bring with them a number of air pollution problems.

The removal and / or conversion of these impurities is effected catalytically by hydrogenation treatment in which a catalyst feed containing sulfur and nitrogen contents comes on a carrier in the presence of hydrogen in Berunning. The treatment conditions can a wide range of temperatures. Include pressures and space velocities that can be determined by the equipment of the technical refineries.

Supported catalysts contain metallic components supported on a refractory inorganic oxide support of synthetic or natural origin, and have a medium to high effective surface area and a well-developed pore structure. Catalytically active metals can be applied to a shaped or unshaped carrier by a known impregnation method for the production of carrier analyzer. Then that usually follows Molding (if necessary) and calcination to convert the catalytic metal compounds to the oxides. Various proposals have been made for the preparation of active catalysts for hydrogenation treatment known through individual impregnation techniques with acid-stabilized solutions of the catalytically active metal components.

In US-PS 38 40 472 the production of a Impregnation solution described, the promoter solution consisting essentially of molybdenum oxide and at least one special metal compound of metals of group VIII and phosphoric acid dissolved in water. The solution has molar ratios for P / Mo im Range from 0.1 to 2.5.

The invention is based on the object of a nickel-molybdenum catalyst for the hydrogenation treatment of hydrocarbons and a catalyst for the same Manufacture to provide a suitable method, which is characterized by a high desulfurization and denitrogenation and in particular shows a particularly high desulfurization activity. In addition, catalysts were aimed at those high Metal loads lead to extremely high activity, i.e. the activity of the catalyst through the high metal loading is not affected.

To achieve the object, the catalyst specified in claim 1 is used for the hydrogenation treatment proposed by hydrocarbons, which is distinguished by a special composition and is manufactured using a special impregnation technique. Claim 2 gives a method for producing the Catalyst on. The use of the new catalyst according to claim 3 is a further object of Invention.

Particularly proven advantageous compositions of the catalyst correspond to the following approximations:

(I) 26.1 wt% MoOj. 6.41 wt% NiO and 3.1 wt% P2O5.

(2) 26.1 wt% MoOi. 5.59% by weight NiO and

J.6% by weight P ₂ O ₅ .

(3) 25.4 wt .-% MoO .5.29 ₁ wt .-% NiO, and

1.7% by weight P ₂ O ₅ and

(4) 232 wt% MoO j. 5.24% by weight NiO and

13 wt.% P ₂ Ov

The catalysts for hydrogenation treatment are made according to the invention by applying a multiple impregnation and a critical one Ratio of molybdenum to nickel. The catalysts show a higher than normal activity in the Removal of contaminants from hydrocarbon feeds, especially when removing both sulfur and nitrogen levels. They contain relatively little P2O5 your Use enables the use of lower effective operating temperatures for a given percentage removal of impurities, e.g. B. at an 85% removal of sulfur.

The invention uses a new stabilized impregnation solution to prepare the catalysts for the hydrating treatment of throat hydrogen fillings, which consists essentially of an aqueous solution of the molybdenum and nickel in such proportions is that the molar ratio of molybdenum to nickel is approximately 3: 1. The solution st by adding a stabilized by a small amount of phosphoric acid, which has a molar ratio of phosphorus to molybdenum of 0.087 does not go out.

To produce the catalyst according to the invention, the catalyst support is impregnated in several stages, in which at least one stage is impregnated with this new impregnation solution.

It is cheap to have two impregnations with this new one Carry out impregnation solution and the second impregnation by dipping in the special impregnation solution to execute.

An expedient embodiment of the method provides for the use of an impregnation solution which consists of nickel carbonate and molybdenum trioxide dissolved in water, and a concentration of molybdenum trioxide from 173 g / l to 343 g / l, the stabilizing effect of phosphoric acid with molybdenum trioxide contents over 120 g / l solution has a particularly beneficial effect.

A preferred composition of the impregnation solution contains 288 g / l MOO3, 473 g / l NiO and 12.4 g / l P ₂ O ₅ .

The process of the present invention for preparing the catalyst to be hydrogenated comprises treatment generally the following two-stage impregnation:

a) Two impregnation solutions "A" and "B" are prepared, where solution "A" is molybdenum and Nikkei in the case of acid stabilization with very low acid content. Solution "B" is the solution to one soluble nickel salt.

b) An aluminum oxide or alumina carrier or a carrier made of aluminum oxide-silicon dioxide or Alumina-silica material is impregnated with "A" and "B" or their equivalent.

c) The impregnated material from step (b) is shaped and calcined by a known method.

d) The calcined material from step (c) is impregnated again with solution "A" and a second time calcined

Solution "A" is an essential feature. This solution contains about 3 mol of molybdenum per 1 mol of nickel S and an acid stabilization at a low acid level. In general, the stabilized solution "A" is by mixing the required amounts of the nickel and molybdenum components in water with the acid stabilizer The mixture is then heated and allowed to react sufficiently to form a clear solution to obtain. Normally, dks takes several hours at 82 ° C or above. The volume of the Solution can be adjusted to the desired concentration with water.

The salts of nickel, in particular nickel carbonate, are expediently used in the impregnation solution used. Suitable molybdenum compounds are the molybdenum oxides. In particular, molybdenum trioxide is used used

Phosphoric acid can be used as an acid stabilizer.

Solution "A" is advantageously prepared with nickel carbonate, molybdenum trioxide and phosphoric acid. Ni-Mo solutions of 120 g / 1 MoO ₃ concentration or less are stable for 24 hours without the addition of phosphoric acid. For concentrations higher than 120 g / l MOO3 it is necessary to add a small amount of phosphoric acid to stabilize the solution for 24 hours. The concentration of the metals in the special solution "A" can be varied within a range from 173 g / l to 340 g / l MOO3 with a maximum of 20.1 g / l required for stabilization. This corresponds to a maximum molar ratio of P / Mo of 0.087. Solution "B" is the aqueous solution of a soluble nickel salt. Nickel citrate is particularly useful.

Any known alumina / alumina or silica / alumina / alumina carrier for hydrogenation treatment can be used for catalyst production.

Methods for impregnating the catalyst support are known from the art (see e.g. US-PS 32 32 887). The first impregnation in the preparation of the catalyst is expediently hydrothermal But also other processes, such as pore volume impregnation or the common rumble lie within the concept of the invention. The second pin impregnation can be carried out by known methods for dispersing metals on a shaped support. The best practices are dipping or pore volume impregnation. Particularly Dip impregnation is appropriate.

The catalyst shaping can be carried out by known methods. Extrusion and spheridization are the cheapest methods.

Manufacture of impregnation solutions

Solution "A" (288 g / l MoO ₃ , 473 g / l NiO and 12.4 g / l P2O5) were prepared as follows:

A slurry was made of 9000 ml of H ₂ O (21 ⁰ C) 2880 g Mooj and 144 ml of 75 ° / H3PO4 cent applied. Nickel carbonate (820 g) was added over a period of 15 minutes. The mixture was heated to 93 ° C. with agitation and held at that temperature for 2 hours. A clear green solution resulted. The solution had a pH of 3.0 and a P / Mo molar ratio of 0.087. The volume of the solution was adjusted to 101 with water. The solution was stable indefinitely (at least 6 months at room temperature).

Solution "Β" (106 g / l NiO) was prepared as follows: Anhydrous citric acid (80 g) was dissolved in 350 ml H ₂ O "(24 ° C). Nickel carbonate (73.3 g) was then added over a period of 15 The slurry was heated slowly to 82 ° C. with continued agitation After 1 hour of reaction at 82 ° C., all of the NiCO ₃ had dissolved and the pH was 3.8, and the volume of the solution was adjusted to 400 ml with water

Three variants of the solutions "A" were prepared in order to determine the required range of phosphoric acid, which is necessary to obtain stable Ni-Mo solutions of various metal concentrations

Variant 1 ("A")

A Ni-Mo solution of 120 g / l MoO ₃ and 19.8 g / l NiO as metal concentration was prepared according to method “A” above. No phosphoric acid was added

In preparing the solution, 5400 ml H2O (27 ° C), 720 g MoO ₃ and 203 g NiCO ₃ slurried The mixture was agitated and heated to 88 After 2 h at ⁰ C 88 ⁰ C gave a clear green solution. The volume of the solution was adjusted to 6000 ml with water. This solution was stable for about 24 hours, after which a green solid precipitated.

Variant 2 (»A«)

30th

This solution was prepared like variant 1, but with the addition of 36 ml of 75% H ₃ PO ₄ to the final solution of 6000 ml. This solution (120 g / l MoO ₃ , 19.8 g / l NiO and 5.15 g / l P ₂ Os) was stable for at least 45 days at room temperature. The P / Mo molar ratio of the solution was 0.087.

Variant 3 (»A«)

This solution was made using the procedure above for Solution "A", but with a change in the amount of reactants. The quantities were 900 ml H ₂ 0.340 g MoO ₃ , 96 g NiCO ₃ and 17 ml 75% H ₃ PO ₄ . The solution was adjusted to 1000 ml with water and was stable for at least 45 days. The P / Mo molar ratio of the solution was 0.087. The concentration of the metal components in the final solution was 340 g / l MoO ₃ , 56 g / l NiO and 14.6 g / l P ₂ O ₅ .

example 1

10

15th

20th

25th

50

This example illustrates the preparation of a catalyst according to the invention. This example uses solution "A", which contains 288 g / l MoO ₃ and has a P / Mo molar ratio of 0.087

15.23 kg of alumina / silica powder containing 22% solids were slurried in 4 liters of water. The alumina / silica contained 2.8% SiO ₂ on a dry basis, the remainder being essentially Al ₂ O ₃ . The slurry was mixed with 2522 ml of solution "A" and 844 ml of solution "B". The slurry was heated to 93 ⁰ C and 1 h at 93 ° C held After impregnation, the slurry was filtered. The filtrate was saved. The filter cake was dried at 82 ° C. for 2 hours. The impregnated dried filter cake had a free moisture content of 42%. 8.17 kg of the dried filter cake was placed in a mixer. The filtrate (3800 ml) was added to the mixer. The material was mixed for 20 minutes and then pressed through a 1.85 mm die at 55% free moisture. The extrudates were predried for 3 hours at 149 ° C. and then calcined for 2 hours at 593 ° C. The calcined, impregnated extrudates contained after the first impregnation 17% MoO ₃ , 3.73% NiO and 0.78% P ₂ O ₅ (in each case percent by weight). 2 ^ 7 kg of the above extrudate was for 16 hours in 9080 ml of solution "A" dipped After impregnation, the solution was drained, and the impregnated catalyst at 149 ⁰ C dried and then 2 hours at 593 ° C calcined

The finished catalyst contained 28% MoO ₃ , 6.4% NiO and 3.1% P ₂ O ₅ (in each case% by weight). The chemical analyzes can be found in the table.

Example 2

This example works as in Example 1 however, the immersion time is reduced from 16 hours to 1 hour. All other catalyst preparation steps are the same same as in example 1. Find the turf results yourself in the table.

Example 3

The catalyst was prepared in the same way as the catalysts in Examples 1 and 2, only the metals in the calcined extrudate after the first impregnation were 11.8% by weight MoO ₃ , 3.51% by weight NiO and 0, 50 wt% P ₂ O ₅ . After an immersion time of one hour for the second impregnation, the finished catalyst contained 26.2% by weight MoO ₃ , 5.59% by weight NiO and 1.6% by weight P ₂ O ₅ . The analysis results are given in the table.

Example 4

In this example, the metal content is further reduced after the first impregnation, so that the extrudate after the first impregnation is 5.9% by weight MoO ₃ , 3.08% by weight NiO and 0.05% by weight P ₂ O ₅ contains. In addition, the metal impregnation of the first stage was carried out by adding the metal compounds MoO ₃ , NiCo ₃ and citric acid in their solid form instead of solutions "A" and "B". In all other points, the preparation of the finished catalyst followed the procedure described in Examples 2 and 3. The finished catalyst contained 23.6% by weight of MOO3, 5.76% by weight of NiO and 1.3% by weight of P ₂ O ₅ . The analysis results are summarized in the table.

Example 5

The procedure of Example 4 was followed, but only nickel carbonate and citric acid were used to impregnate the alumina-silica support. The extrudates impregnated in the first stage contained 2.85% by weight NiO and the catalyst impregnated in the second stage contained 22.8% MoO ₃ , 5.85% by weight NiO and 1.4% by weight =% P2O5. The analysis results are given in the table.

Example 6

The extrudates calcined after the impregnation of the first stage were prepared according to the method in Example 3

procedure described. At the second stage impregnation 454 g of the calcined extrudate in 1816 ml of impregnation solution "A" with a concentration of 200 g / l MoOi dipped (instead of the 288 g / l MoO] as in Example 3). The analysis results are given in the table.

Example 7

This catalyst was prepared by the same method as in Examples 3 and 6, but with a value of the concentration of solution "A" 120 g / l MoOj in the final impregnation step. The analysis results are given in the table.

Example 8

This example shows the use of pore volume impregnation in the second stage. The calcined extrudates obtained after the first-stage impregnation were prepared by a method similar to Example 1 and gave a material which contained 14, b% by weight of MoOj. 4.55 wt% NiO and 0.93 wt% P ₂ O-. This carrier (7302 g) was impregnated with 4554 ml of solution "A" (288 g / l MoOj) by introducing the liquid into an evacuated mixed drum bed of the extrudate. The impregnated extrudates were dried and caicinated for 2 hours at 593 ° C. The analysis results are given in the table.

Application examples

The catalysts of Examples 1 through 8 were tested for hydrotreatment activity. The activities were determined in comparison with a commercially available Ni-Mo hydrotreating catalyst. The analysis of the comparative catalyst is given in the table. 60 ml of each of the test catalysts to be evaluated and of the comparative catalyst were treated with a high-boiling vacuum gas oil (API density 20.0: boiling range 394.5-575 ° C) containing 2.8% by weight sulfur and 1560 ppm nitrogen, tested. The test conditions were 357 ° C, 7 MPa overpressure, LHSV 1.5 volumes ö | / h / vol. Catalyst and 0.73 Nm ³ /! Hydrogen. The catalysts were placed in adjacent tubular reactors in an isothermal sand bath.

The comparative catalyst received a standard activity value of 1.00 on a volume basis. The Activities of the experimental catalysts are given as relative values with respect to this standard on a volume basis. The activity results are summarized in the table.

A catalyst according to the invention, prepared according to Example 1, was used with a commercially available Co-Mo catalyst, in the desulfurization of a mixture of a vacuum gas oil and a vacuum residue compared.

The catalysts (1.59 mm extrudates) were with

the same volumes in identical tubular reactors of an electrically heated test facility and one subjected to standardized presulfiding activation treatment and a stream of that described below Feed mixture exposed for desulfurization. The reactor temperatures were if necessary raised to maintain 85% desulfurization, and the trial was under for 24 days continued under the conditions set out below. Maintaining the superior activity of the Catalyst according to the invention can be seen both on the basis of a lower operating temperature, as well as a smaller temperature rise over the extended Period of operation.

Charging properties (mixture)

Density. ⁰ APl Test conditions 25.7 Flash point. "C (COC) Trial start temperature 152 Kamsbottom carbon, wt% Reactor pressure i, 9i Sulfur, wt% 0.62 Nitrogen, wt% 0.114 Distillation: Initial boiling point, ⁰ C 214.1 10% 300 50% 399.0 90% 568.5 365.5 ° C 8.555 MPa

LHSV (space velocity of oil liquid) 1.74
Ratio hydrogen / oil 0356 Nm ³ /!

Properties of the inventive caialyzer (Example 9)

MoOj 50 5 27% Comparison NOK 55 10 6.7% catalyst P ₂ O ₅ 15th 2.25% 372 45 20th 0.92 g / ml 378.5 24 383 For 85% desulphurisation 386 Medium bulk density required temperature. ° C 388 Activity results Catalyst the Days of operation invention 370 374 376.5 378 3785

Table I.

Analytical and activity results for hydrotreatment catalysts

Hoi 2 J 4th 5.9 5 b 7th 8th Ver game 3.08 same I. 0.05 Metal analysis according to ei sier Impregnation and 17.0 11.8 - 11.8 11.8 14.6 Calculation (G cw .- "'!>) 3.73 3.51 2i.b 2.85 3.51 3.51 4.55 MoO, 17.0 0.78 0.50 5.7b 0.0b 0.50 0.50 0.93 - NOK 3.73 1.3 - Ρ.Ό-, 0.78 1.20 - Metal analysis after / next 25.4 2b.2 1.14 22.8 23.2 21.1 23.8 Impregnation (wt. ■%) 5.29 5.59 0.92 5.85 5.24 5.0 5th bl MoO, 28.0 1.7 l.b 1.4 1.5 1.2 1.7 19.9 NOK b.41 1.23 1.39 1.15 1.43 1.22 1.23 5.4 P: O-, 3.1 1.19 1.29 1.09 1.17 1.07 1.0 b.3 HDS activity volume 1.30 0.89 0.91 0.8b 0.87 0.82 0.85 1.00 HDN activity volume 1.1b 1.0 Average bulk density g / ml 0.93 0.88

Claims (1)

Patent claims: 1. Catalyst for the hydrogenation treatment of hydrocarbons, obtainable by impregnating a support made of aluminum oxide or alumina _{, optionally containing SiO 2, with a stabilized nickel.} Solution containing molybdenum and phosphorus, subsequent drying and calcining, characterized in that the catalyst contains 21 to 30% by weight MoO ₃ .5 to 7% by weight NiO and 1.0 to 3.5% by weight P2O5 and is obtained by shaping the impregnated carrier and impregnating it again after calcining, drying and calcining it, in at least one of the impregnation stages being impregnated with a solution which contains the compounds of nickel and molybdenum and phosphoric acid and in which the molar ratio of molybdenum to nickel is about 3: 1 and the molar ratio of phosphorus to molybdenum does not exceed 0.087