Catalyst, process for its production (options) and how hydroperiod hydrocarbons

 

(57) Abstract:

The invention relates to catalysts containing on the surface of the carrier compounds of molybdenum and/or tungsten, with or without additives compounds of one or more transition metals, processes for their preparation and may find wide application in the processes of hydroperiod hydrocarbons of petroleum or coal origin. The invention solves the problem of obtaining a highly active sulfide catalysts without using Ozernaya agents. The task is solved by a catalyst composition containing a surface active component carrier in the form of complex compounds, which includes a composition of molybdenum and/or tungsten General formula {MnSmOx(H2O)y}, where M=Mo and/or W, n=1-6, m=1-24, x=0-12, y=0-6, in combination with one or more compounds of metals of the first transition series. In the first embodiment the catalyst is prepared by sequential attachment to the first surface of the carrier compounds of molybdenum and/or tungsten with sulfur-containing ligands and subsequent consolidation of one or more metals of the first transition series. The second option made the catch of the first transition series with the subsequent fastening of compounds of molybdenum and/or tungsten with sulfur-containing ligands. 4 N. and 8 C.p. f-crystals.

The invention relates to catalysts containing on the surface of the carrier compounds of molybdenum and/or tungsten, with or without additives compounds of one or more transition metals, processes for their preparation and may find wide application in the processes of hydroperiod hydrocarbons of petroleum or coal origin.

Widely known catalysts for hydroperiod hydrocarbons from oil and coal origin containing catalytically active compounds of molybdenum and/or tungsten and Nickel or cobalt deposited on a porous carrier. These catalysts obtained by impregnation of the support with solutions of various compounds Mo(W) and/or Ni(Co). As media are porous inorganic and carbon materials. The former include the oxides of aluminum, silicon, magnesium, and others, as well as their combinations, such as aluminosilicates, zeolites, etc. Carbon carriers can be either of natural origin or synthetic.

For the deposition of molybdenum on the surface of the carrier using one of the following compounds: heptamolybdate ammonium (U.S. Pat. USA 4318801, C 10 G 045/04, 09.03.82), molybdenum acid (U.S. Pat. USA nesene Nickel or cobalt use salts of mineral or organic acids. After impregnation of the carrier with solutions of these compounds, the catalyst is dried and calcined in air at a temperature of 400-600 C. Thereby obtaining an oxide form of the catalyst.

However, all the processes hydroperiod hydrocarbons from oil and coal origin is performed on the sulfide form of the catalysts. Therefore, the oxide form of the catalyst is transferred to the sulfide form in one of the known methods. A known method of saturation catalysts elemental sulfur with subsequent transfer to the sulfide state in an atmosphere of hydrogen (U.S. Pat. USA 4177136, C 10 G 23/02, 04.12.1979).

There is a method of acarnania by sublimation of elemental sulfur in the atmosphere of hydrogen (U.S. Pat. USA 4943547, B 01 J 027/051, 24.07.90).

The disadvantage of these methods is the difficulty of monitoring the activation processes of sulfur, which leads to loss of catalyst activity. In addition, a significant drawback of all methods acarnania catalysts is the necessity of processing at high temperature oerstedii agents (hydrogen sulfide, mercaptans, organic sulfides, and so on) that are highly toxic, hazardous and require special precautions in their use.

Completely new Pb 01 J 27/02, 23.07.85; 4719195, B 01 J 27/02, 12.01.88; 5139983, B 01 J 37/02, 18.08.92; 5397756, B 01 J 37/20, 14.04.95; 5821191, B 01 J 027/02, 13.10.98). This decision was based on preliminary saturation of the calcined catalysts are organic compounds of polysulfide sulfur with the subsequent transfer of sulfurized catalysts in the sulfide state directly in the catalytic reactor. The advantage of these methods is the strict temperature control during the process acarnania and subsequent transfer catalysts in sulphide form. The disadvantage of these methods is the need to obtain first oxide form of the catalyst, including the stage of impregnation, drying and calcining, as well as the complexity of the synthesis of organic polysulfide sulfur compounds.

Another approach to solve the problem of obtaining catalysts hydroperiod in sulfide form is the use of compounds of molybdenum or tungsten containing in its composition the required amount of sulfur, sufficient for their conversion to the sulfide state without additional Ozernaya agents. Such compounds can be molybdenum compounds of General formulax[Mo3Sz], mainly IN2[Mo3(S2)6S], where In - monovalent UB>S4(U.S. Pat. USA 4728682, 01 17/42, 01.03.88). Known to produce catalysts using tetrathiotetracene complexes of molybdenum and tungsten of General formula (NR4)x[M(MoS4)2] and (NR4)x[M(WS4)2] (U.S. Pat. USA 4581125, C 10 G 45/08, 8.04.86). The advantage of this approach is the lack of need for sulfide shape of the catalysts with the use of sulphur as sulphide form catalysts are simply heating the catalyst in a hydrogen atmosphere. The disadvantage is the complexity of the synthesis of the desired compounds.

The closest is the catalyst hydroperiod hydrocarbons of petroleum or coal origin, containing on the surface of the carrier of the active component from compounds of molybdenum and compounds of Nickel or cobalt, compound of molybdenum comprises a surface atoms of the medium and has the General formula:

(A)-[MoOmLx(H2O)y],

where a is the surface atoms of the material of the carrier,

L is a ligand, representing a compound in deprotonated form, selected from the group comprising H2O, mineral acids, carboxylic acids, alcohols, diketones.

Cuttle or cobalt. After drying, the catalyst sarnaut in H2S at 400 to obtain a sulfide form of the catalyst (U.S. Pat. RF 2052285, B 01 J 21/04, C 10 G 45/08, 15.06.93).

By virtue of the known catalyst is its high activity in the reaction, hydrogenolysis of C-S-link, which is key when hydroperiod hydrocarbons. The disadvantage of this method of cooking is the need of the use of hydrogen sulfide to acarnania catalyst.

The invention solves the problem of obtaining a highly active sulfide catalysts without using Ozernaya agents.

The problem is solved by the composition of the catalyst for hydroperiod hydrocarbons from oil and coal origin containing on the surface of the carrier, the active ingredient in the form of complex compounds, which includes a composition of molybdenum and/or tungsten and the metal of the first transition series, the said catalyst contains on the surface of the carrier composition composition {MnSmOx(H2O)y}, where M=Mo and/or W, n=1-6, m=1-24, x=0-12, y=0-6, in combination with one or more compounds of metals of the first transition series.

The problem is solved also two variants of the method of prepara what about the attachment to the first surface of the carrier compounds of molybdenum and/or tungsten with sulfur-containing ligands of General formula {MnSmOx(H2O)y}, where M=Mo and/or W, n=1-6, m=1-24, x=0-12, y=0-6, with subsequent fixation of one or more metals of the first transition series.

According to the second variant it is prepared by successive attachment to the first surface of the carrier compounds of one or more metals of the first transition series with the subsequent fastening of compounds of molybdenum and/or tungsten with sulfur-containing ligands of General formula {MnSmOx(H2O)y}, where M=Mo and/or W, n=1-6, m=1-24, x=0-12, y=0-6.

Compounds of molybdenum and/or tungsten with sulfur-containing ligands can be obtained by dissolving a mixture of oxide compounds of these metals with elemental sulfur in the solution of hydrazine and/or its derivatives. Compounds of molybdenum and/or tungsten with sulfur-containing ligands can also be obtained by dissolving the oxide compounds of these metals in the solution of polysulfide sulfur.

The solution of polysulfide sulfur is obtained by dissolution of elemental sulfur in the solution of hydrazine and/or its derivatives. The catalyst can optionally be heated in a reducing and/or inert atmosphere at a temperature not exceeding 500 C.

The essence of the present invention is poly tungsten with sulfur-containing ligands of General formula {MnSmOx(H2O)y}}, where M=Mo and/or W, n=1-6, m=1-24, x=0-24, y=0-6. In this event, the sulfide form of the catalyst occurs by thermal decomposition of these surface compounds in a reducing and/or inert atmosphere without the use of additional sources of sulfur.

The synthesis of the catalysts is carried out in two ways, based on the synthesis of water-soluble complexes of molybdenum and/or tungsten with sulfur-containing ligands of General formula {MnSmOx(H2O)y}, where M=Mo and/or W, n=1-6, m=1-24, x=0-12, y=0-6. For example, a mechanical mixture of solid compounds of molybdenum and/or tungsten in oxide form elemental sulfur dissolved in an aqueous-ammoniacal solution of hydrazine and/or its derivatives. The resulting red solution of the complex in contact with a solid carrier with the bleaching solution, indicating that the adsorption of the mentioned surface of the carrier. Then the precursor of the active component is applied compound of the metal of the first transition series, such as Nickel acetate or cobalt. After drying the catalyst at a temperature of 100-150, it is heated, for example, in the atmosphere is a group of active component in the sulfide form.

The task is also solved by way of hydroperiod hydrocarbons of petroleum or coal origin, the main feature of which is the use of the above catalyst.

The invention is illustrated by the following examples.

Example 1 (the prototype)

The catalyst of comparison (Co,Mo)/Al2ABOUT3prepared according to the method described in U.S. Pat. RF 2052285. For this purpose, the aluminum oxide treated with an aqueous solution of molybdenum oxalate (NH4)2[Mo2O4(C2O4)2(H2O)2]. Then on molybdenum-containing media put the acetate of cobalt from aqueous solution. After drying of the catalyst in air at 140 With its sarnaut in the hydrogen sulfide to obtain a sulfide form of the catalyst. The catalyst was tested in the reaction, hydrogenolysis of thiophene, which is a common test for sulfide catalysts hydroperiod hydrocarbons from oil and coal-chemical origin. Activity is measured in running the installation under hydrogen pressure of 20 ATM and at a temperature of 300 C. the Activity is 35 {mol (C4H4S)/mol (Co+Mo) h}.

Example 2

The catalyst (Co,Mo)/Alth sulfur in a molar ratio of 1:2.5 is dissolved in an aqueous-ammoniacal solution of hydrazine hydrate is added N2H5OH. According to EXAFS, NMR and IR spectroscopy the complex has the following structure:

This solution of the complex process of the alumina of example 1, and then the obtained molybdenum-containing media put cobalt acetate analogously to example 1. After air drying the catalyst loaded into the reactor and heated in an atmosphere of hydrogen to 300 C. Additional stage acarnania is not required.

The catalyst was tested in the reaction, hydrogenolysis of thiophene, which is a common test for sulfide catalysts hydroperiod hydrocarbons from oil and coal-chemical origin. Activity is measured in running the installation under hydrogen pressure of 20 ATM and at a temperature of 300 C. the Catalyst has an activity 43 {mol (C4H4S)/mol (Co+Mo) h}.

Example 3

The catalyst (Ni,Mo)/Al2O3prepared in several stages. First, a mechanical mixture of molybdenum acid, H2Moo4and elemental sulfur in a molar ratio of 1:4 is dissolved in a water-ammonia solution asymmetrical diethylhydrazine (C2H5)2N-NH2. Then, the resulting red solution is treated with aluminum oxide from example 1, posuisti loaded into the reactor and heated in a hydrogen atmosphere up to 300 C. Additional stages of acarnania is not required. The catalyst was tested in the reaction, hydrogenolysis of thiophene. The catalyst has an activity 46 {mol (C4H4S)/mol (Ni+Mo) h}.

Example 4

The catalyst (Ni,W)/SiO2prepared in several stages. First, a mechanical mixture of tungstic acid, H2WO4and elemental sulfur in a molar ratio of 1:6 is dissolved in an aqueous-ammoniacal solution of hydrazine hydrate is added. The synthesized compound has the structure similar to the complex of example 2, only the terminal oxygen atoms are replaced by sulfur atoms, and the gross formula of the complex can be represented in the form (N2H5)2[W2S4(S4)2(H2O)2]. Then a solution of the obtained complex is treated with silica gel, is the discoloration of the solution and staining medium red. The resulting tungsten-containing silica gel treated with an aqueous ammonia solution of Nickel nitrate and after drying, the catalyst was heated in nitrogen atmosphere to 500 C. Additional stage acarnania is not required. The catalyst has an activity 41 {mol (C4H4S)/mol (Ni+W) h}.

Example 5

The catalyst (Fe,Mo)/C is prepared in several stages. At first it is of rainheart. Then this solution is dissolved solid paramolybdate ammonium (NH4)6Mo7O244H2O. the Resulting red solution is treated with carbon media. Then molybdenum-containing media is treated with ferric chloride solution, and after drying, is heated in argon atmosphere up to 300 C. Additional stage acarnania is not required. The catalyst has an activity 21 {mol (C4H4S)/mol (Fe+Mo) h}.

Example 6

The catalyst (Co,Mo,SG)/Al2O3SiO2Gprepared as follows. Silica-alumina carrier is impregnated with a solution of chromium chloride, dried and calcined in air. Then prepare a mechanical mixture of Moo3and elemental sulfur in a molar ratio of 1:12, is dissolved in an aqueous-ammoniacal solution of hydrazine hydrate is added and the resulting solution is impregnated with the chrome-containing medium, then applied cobalt from a solution of cobalt chloride. After air drying, the catalyst is heated under a layer of diesel fuel to a temperature of 350 C. the Catalyst was tested in the Hydrotreating of diesel fuel at a temperature of 350 C and a hydrogen pressure of 40 ATM. The initial sulfur content in diesel fuel - 1.1 wt.%, the final sulfur content is less than 0.05 wt.%.

5-C24.

Example 8

(Co,Mo,W)/Al2O3. - Tungstic acid is dissolved in the solution of polysulfide sulfur, which is prepared by dissolving elemental sulfur in the solution of gersinhomala. Then this solution is treated with alumina of example 1. After drying, the tungsten-containing media is treated with a solution of a molybdenum complex prepared by dissolving a mixture of elemental sulfur and paramolybdate ammonium in solution of hydrazine hydrate is added in a molar is remaut in the flow of gasoline under hydrogen pressure of 30 ATM at a temperature of 300 C. Processing is subjected to the raw material reforming unit with a sulfur content of 0.05 wt.%. At the outlet of the catalyst bed get gasoline fraction with a sulfur content of 15 ppm.

Thus, as seen from the above examples, the proposed catalyst has a high activity in the processes of hydroperiod hydrocarbons, in the way of its preparation, there is no stage of acarnania using toxic sulfur compounds.

1. The catalyst for hydroperiod hydrocarbons from oil and coal origin containing on the surface of the carrier, the active ingredient in the form of complex compounds, which includes a composition of molybdenum and/or tungsten and the metal of the first transition series, characterized in that the catalyst contains, on the surface of the carrier composition composition {MnSmOx(H2O)y}, where M=Mo and/or W, n=1-6, m=1-24, x=0-12, y=0-6, in combination with one or more compounds of metals of the first transition series.

2. The preparation method of catalyst for hydroperiod hydrocarbons from oil and coal origin, fixing on the carrier surface of the active component in the and of the first transition series, characterized in that it is prepared by successive attachment to the first surface of the carrier compounds of molybdenum and/or tungsten with sulfur-containing ligands of General formula {MnSmOx(H2O)y}, where M=Mo and/or W, n=1-6, m=1-24, x=0-12, y=0-6, with subsequent fixation of one or more metals of the first transition series.

3. The method according to p. 2, characterized in that compounds of molybdenum and/or tungsten with sulfur-containing ligands obtained by dissolving a mixture of oxide compounds of these metals with elemental sulfur in the solution of hydrazine and/or its derivatives.

4. The method according to p. 2, characterized in that compounds of molybdenum or tungsten with sulfur-containing ligands obtained by dissolution of the oxide compounds of these metals in the solution of polysulfide sulfur.

5. The method according to p. 4, characterized in that the solution of polysulfide sulfur is obtained by dissolution of elemental sulfur in the solution of hydrazine and/or its derivatives.

6. The method according to any of paragraphs.1-5, characterized in that the catalyst is heated in a reducing and/or inert atmosphere at a temperature above 500C.

7. The preparation method of catalyst for hydroperiod hydrocarbon oil is a metallic compound, which includes a composition of molybdenum and/or tungsten and the metal of the first transition series, characterized in that it is prepared by successive attachment to the first surface of the carrier compounds of one or more metals of the first transition series with the subsequent fastening of compounds of molybdenum and/or tungsten with sulfur-containing ligands of General formula {MnSmOx(H2O)y}, where M=Mo and/or W, n=1-6, m=1-24, x=0-12, y=0-6.

8. The method according to p. 7, characterized in that compounds of molybdenum and/or tungsten with sulfur-containing ligands obtained by dissolving a mixture of oxide compounds of these metals with elemental sulfur in the solution of hydrazine and/or its derivatives.

9. The method according to p. 7, characterized in that compounds of molybdenum or tungsten with sulfur-containing ligands obtained by dissolution of the oxide compounds of these metals in the solution of polysulfide sulfur.

10. The method according to p. 9, characterized in that the solution of polysulfide sulfur is obtained by dissolution of elemental sulfur in the solution of hydrazine and/or its derivatives.

11. The method according to any of paragraphs.7-10, characterized in that the catalyst is heated in a reducing and/or inert atmosphere at a rate which ashodaya in the presence of a catalyst, containing on the surface of the carrier, the active ingredient in the form of complex compounds, which includes a composition of molybdenum and/or tungsten and the metal of the first transition series, characterized in that the use of the catalyst according to any one of paragraphs.1-11.

 

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