Method for pretreatment of the catalyst in the hydrocarbon processing outside of the reactor


(57) Abstract:

Describes how pre-treatment of the catalyst in the hydrocarbon processing by sulfanilamide, namely, that out of the catalytic reactor is introduced into the mass of catalyst sulfureuse agent, process the catalyst with hydrogen at a temperature of 150 - 700oWith, Passepartout catalyst. The technical result is simplification. 8 C.p. f-crystals, 1 table.

The present invention relates to a method of pre-treatment or activation of the catalyst hydroconversion hydrocarbons, including the original pre-sulfonation catalyst out of the reactor. The catalyst thus activated under the action of hydrogen in the reactor the conversion of hydrocarbons, a ex situ (outside the reactor) in the presence of hydrogen, and then also ex situ (outside the reactor) is placed at the air before further transportation, and then loaded into the reactor conversion of hydrocarbons.

Typically, prior art before using a new or regenerated catalyst is subjected to sulfonation (prior to sulfonation), carried out in the reactor of hydrobromide. This sulfonation allows Dov formula (depending on the metals present) Co9S8, MoS2WS2and Ni3S2. In fact, the active phases of these catalysts are mixed sulfides, whereas new or regenerated catalysts include the oxides.

This sulfonation (pre-sulfonation) prior art is carried out at a temperature close to or higher (above 180oC and more preferably above 250o(C) in relation to the reaction temperature chosen for the reaction hydrodesulphurization unit, hydrocracking or hydrogenation, for several hours, with application of a mixture of serosoderjaschei compounds, usually diluted with hydrogen.

Currently, the regeneration of catalysts are increasingly carried out by the specialist regeneration of catalysts, sometimes far from industrial installations. However, specialist refining it seems reasonable to obtain ready-to-use product that allow you to make effective ways of European patents EP-B-130850 and EP-B-181254 the same applicant, where structurae compound is introduced into the catalytic mass, and the above connection causes sulfonation or pre-sulfonation catalyst, and then in the reaction zone (zone processing ishodnikami of course, the introduction of the above serosoderjaschei connection, if necessary, can be done near industrial plants or even at the place of processing of the catalyst; the method of introducing the above serosoderjaschei connections can be made outside of the reactor in relation to the new or regenerated catalyst before its use in the industrial setting.

The installation of refining or any installation that uses the catalyst, this catalyst was then activated in the reactor the conversion of hydrocarbons in the presence of hydrogen at a temperature of, for example, 250-350oC (if, for example, catalyst desulfurization do in order to enter in the interaction of sulfur with contained metals and immediately start the reaction processing or conversion of hydrocarbons by injection of the processing load).

The present method according to the invention allows to improve the activation of the catalyst and is characterized by the treatment of the catalyst in the presence of hydrogen outside the reactor, followed by contacting of the catalyst with air in order to realize oxidizing passivation of the catalyst. After this stage, the catalyst is directed to the process oil is LASS="ptx2">

Thus, according to the invention carry out a preliminary treatment of the catalyst according to the method outside of the reactor, including:

-introduction sulfureuse agent in the catalytic mass,

treatment with hydrogen catalyst at a temperature of 150-700oC,

the passivation of the catalyst.

The catalysts according to the invention, for example, may include the media-type alumina or modified alumina (fluorine, chlorine, boron, silicon) or other media on the basis of at least one metal oxide or metalloid (magnesium oxide, silica, silica - alumina, silica - magnesia, clay, coal or a mixture of these components), and these carriers, at least in part, may be in amorphous form or in crystalline form (zeolites), and the catalyst includes, in addition, 0.2 to 40%, of at least one active metal VI, VIII, or other groups that choose, for example, in the group consisting of cobalt, molybdenum, Nickel and tungsten. Usually use a couple of two of these metals, for example one of the pairs: cobalt-molybdenum, Nickel-molybdenum, Nickel-tungsten. If necessary you can also use a noble metal VII:

a) in the introduction, outside the reactor, the catalytic mass in its pores at least one sulfureuse agent, and this agent is structurae compound selected in the group consisting of elemental sulfur, organic polysulfides (described in European patent EP-B-130850 and in the European patent EP-B-181254), hydrogen sulfide (H2S), mercaptans, carbon disulfide CS2, sulfides, disulfides, thiophene compounds, or any other compounds whose molecules contain sulfur, which can decompose under the action of hydrogen emitting especially hydrogen sulfide (preferably choose sulfur, organic polysulfides, dimethyl sulfide (DMS) and dimethyl disulfide (DMDS). You can use at least one solvent, for example, white spirit or dearomatizing or no gasoline (as described in European patents EP-B-130850 and EP-B-181254) and/or at least any other appropriate solvent, and in particular, at least one component containing carbon due olefinic type, for example, such a component, as described in European patent EP-A-564317; as an example it is possible to use a mixture comprising 0.1 to about 99.9 wt. % white spirit or equivalent is or equivalent solvent and 2-98 wt. % of at least one of the above compounds or components oleic type. Typically, these component used individually or in mixtures, may be a hydrocarbon go any hydrocarbon fraction can contain a double bond. It may be olefins (monoolefinic, diolefin or polyolefins) or petroleum fractions, can contain olefins as fractions originating from some methods of refining oil, especially as visco - recovery coking, steam cracking. This component preferably may be of the type triglycerides of unsaturated fatty acids, vegetable oils.

When the above compound or component chosen among components of vegetable oils, it is particularly belongs to the family of triglycerides of fatty acids. From oils especially can be called such, are produced from unsaturated fatty acids, such as ethylene acid, for example Mirandolina, Palmanova, oleic, elaidic (geometrical isomer of oleic acid), gadolinia, erucic acid; polyethylene acid (polyethylene acid oils, such as linoleinovoy acid, linolenic acid), and these oils can also soda is Renova, myristic, palmitic, stearic, arachnid acid. Also a component part of a mixture (combination of solvents) may be a complex compound of a fatty acid ester, and the acid portion of the ester contains 6 to 24 C-atoms and one, two or three bonds of olefinic type; or on the basis of rapeseed, peanut, soybean, corn, sunflower, safflower, palm, linseed oils, or animal fats - lard or melted lard. As indicated above, the preferred oils are rapeseed, peanut, soybean, corn, sunflower, safflower, palm, linseed oil.

Introduction sulfureuse agent is carried out in intervals of temperatures, including, for example, temperatures from 0 to 200oC (even 30-200oC).

Sulfureuse agent, therefore, is introduced into the catalytic mass in relation to the chosen temperatures above or by melting and/or sublimation, or by dissolving or else in the form of a suspension, or by passing sulfureuse agent in the form of a gas phase, or partly in one way and partly in another of the ways mentioned above. It can be entered in the absence of solvent or other additives:
oC and preferably above 120oC. This treatment is recommended in some cases, especially when the catalyst is introduced into contact with sulfurous agent and a liquid containing, if necessary, a solvent type white spirit or similar solvent and the olefinic compound type; thus obtained mixture is subjected to heat treatment, with the aim, on the one hand, removing the solvent, on the other hand, especially to cause reaction of the accession of sulfur to the double bonds of olefinic compounds. The heat treatment is carried out at a temperature above 100oC and preferably above 120oC. If sulfurous agent is elemental sulfur, thus partially or completely she joins in the form of polysulfide. This reaction is analogous reaction, which is known in any other field of technology, for example in industry for the manufacture of car tyres, called vulcanization operation. This operation is used to improve the mechanical properties of natural rubber, is carried out by adding elemental sulfur to natural rubber with a subsequent heat treatment. Sulfur reacts with the double bonds of the rubber, which is a polyisoprene with about Chora) under the action of hydrogen, pure or diluted (dilution: 1-50% even 2-20% of hydrogen content), treatment of the catalyst at a temperature of 150-700oC and preferably varying between 250 and 600oC (there are usually at atmospheric pressure for several hours, for example 1-10 h). For this stage there is greater flexibility in the choice of operating conditions: temperature selection, gas dilution, select a catalytic layer (fixed layer, a rotating layer, moving the layer, growing a layer of boiling ode, liquid layer), which allows here to make the best possible uniformity in the distribution of sulfurous agent in the catalytic layer, furthermore, from a strictly constant temperature for all grains (granules) layer. Stage can be performed after stages a) and b). It is also possible to carry out simultaneously with stage a), namely, so that the introduction of sulfurous agent and treated with hydrogen is conducted at the same time. Then there is no stage b);

g) if necessary, in the implementation of out-of-reactor (ex situ) cooling the catalyst (typically to room temperature), for example, under the action of a stream of inert gas or withstood the catalyst in an atmosphere of inert gas (e.g. nitrogen);

d) in the implementation of ex situ is it in purging the catalyst with oxygen, preferably diluted (volume concentration less than 30%, even below 10% or below 5%) and/or blowing air in contact with atmospheric air), and this stage (stage), in which process or which there is a partial re-oxidation of the sulphides of the metals contained in the catalyst mass (oxidizing passivation). During this stage, the absorption of oxygen by the catalyst. This stage leads to catalyst activity higher than that observed in the case of other catalysts, in which sulfureuse agent is introduced by known methods of the prior art. Contact of the catalyst with dilute oxygen (or any gas containing oxygen, for example, molecular oxygen) can be performed in two or more periods with a progressive increase in the concentration of oxygen, for example, as an illustration, about 1%, then 5%.

The invention is particularly well suited for conducting sulfureuse agent in the catalysts of hydrobromide, which are then loaded into the reactor in the zone of hydrobromide, then exposed to hydrogen in the same area of hydrobromide.

Other advantages of the method are especially the following: the tee after a simple startup procedure which is injectioni download directly processed at low temperatures, even at room temperature, without any percolation of sulfur. There is a significant chemically discernible difference in the results of the analysis of the catalyst: at the end of the treatment with hydrogen is sulphide (sulfide) phase (phase), i.e., if, for example, the active elements of the catalyst is molybdenum or tungsten or cobalt, or Nickel, there is a sulfide or sulfides type: MoS2(here, therefore, Mo4+corresponds to sulfide), Co9S8WS2, Ni3S2.

"Sulfide" phase in the catalyst treated according to the invention, namely, after the processing of H2clearly identified using photoelectron spectroscopy X (SPX), which, for example, may show that the molybdenum or tungsten are mainly (usually more than 70%) the oxidation state 4 (type MoS2WS2), while they have full oxidation state 6 (MoO3WO3) fresh or regenerated catalyst, and also for the most part (50%) oxidation number 6 in the catalyst subjected to preliminary sulfonation according to the methods of the prior art, and this after the e between the method according to the invention and methods of the prior art the following: first the user has loaded into your reactor catalyst hydrobromide, containing metals that are chemically was in the form of oxides or in the form of oxysulfides. They were not catalytically active and only in the reactor was formed sulfides. This rate-limiting step in the formation of the active phase can be carried out with difficulty and, in particular, can be uncontrolled and recharacterizing. An advantage of the present invention is direct delivery to the consumer is already active catalyst, the catalytic activity is high before loading into the reactor. The present invention eliminates any danger of achieving optimal catalytic activity in the reactor.

The amount of sulfur included in the catalytic mass in process stage (a), typically corresponds to 50-150% of the amount stoichiometrically required for pre-sulphurization of the active centers of the catalyst, preferably 80-110% and preferably 90-105% of the stoichiometric amount.

On the other hand, passivation, for example, oxidizing, also allows you to eliminate the pyrophoric tendency of these sulfonated phases and, therefore, facilitates the transport of solids in drums or other types of containers. On the other hundred is>/P>The following examples illustrate the invention: comparative examples illustrate different ways of pre-sulfonation level techniques with subsequent activation under the action of hydrogen catalyst in situ in the reactor the conversion of hydrocarbons. Examples according to the invention is illustrated by the same methods pre-sulphurization of the catalyst under the action of hydrogen in the prior art, but then, according to the invention, with activation of ex situ (outside the reactor), and then just ex situ (outside the reactor), with the blowing catalyst diluted with oxygen, then the air before it is loaded into the reactor conversion of hydrocarbons.

Example 1 (comparative)

Use catalyst hydrodesulphurization unit type CoMo in grains (granules) with a diameter of 1.2 mm, containing 19.0 wt. % MoO3and 4.3 wt. % CoO. In the following examples, it is called as A catalyst; it is subjected to prior to sulfonation or sulfonation with sulfur content corresponding to theoretical stoichiometric value for sulphides MoS2and Co9S8. Stoichiometry 100% match of 10.25 wt. % sulfur, based on the value in the dry state, adjusted for the loss in flame.

Catalyst A (1000 g) of the Pach is pore volume (550 ml). Impregnated mass of catalyst was incubated for one hour in a rotating flask in cold, then 2 h at 150oC by evaporation of hydrocarbons and fixation of sulfur organic polysulfide. Thus, get the catalyst B, the characteristics of which are presented in the table.

Example 2 (comparative)

Catalyst A (1000 g) is impregnated with a suspension of 105 g of elemental sulfur, 22 g of rapeseed oil and 330 ml of white spirit, then leave for 1 hour in cold and heated 2 h at 180oC. are Thus obtained catalyst C.

Example 3 (comparative)

Catalyst A (1000 g) is impregnated with a suspension of 105 g of elemental sulfur and 55 ml of white spirit, then leave for 1 hour in cold and heated 2 h at 180oC. are Thus obtained catalyst D.

Example 4

Catalysts B, C, D, prepared according to the descriptions of the previous examples, activate under the influence of hydrogen in a rotary tubular furnace under the following conditions: temperature 400oC, time of 6 h, the gas mixture of hydrogen and nitrogen in a ratio of 5:95, the pressure is normal. At the end of the activation period, the system is cooled and rinsed for 4 h in nitrogen and then rinsed with a mixture of 1% oxygen in nitrogen for 2 h, after which the NGOs of catalysts B, C, D.

Example 5

Catalyst B is treated as in example 4, only at the end stage of activation are purging with nitrogen, but do not oxidizing passivation. The catalyst is placed in the absence of air directly into the flask, filled with white spirit. Thus obtained solid substance H.

Example 6

Sulfonated catalysts A-H explores various methods of measuring the content of carbon, sulfur, loss of flame at 500oC; differential thermal analysis or differential scanning calorimetry - DSC) under hydrogen pressure of 1 bar and at a speed of temperature rise of 5oC in 1 min, analysis by photoelectron spectroscopy X (FASH), catalytic test for hydrodesulphurization unit (GOS) gasoil.

The test conditions are as follows: download: gasoil with initial and final temperatures, respectively 220-370oC, the sulfur content of 0.8 wt. %, the nitrogen content 120 wt. M. D. (ppm by mass), pressure 40 bar, the amount of catalyst 70 ml, the feed rate of the feedstock 140 ml/h, a temperature of 340oC. startup Procedure involves raising the temperature to 320oC at the rate of 140 ml/h of V.N.Karazin the e temperature up to 340oC.

The results of the definitions presented in the table.

Catalysts B and C according to the invention are pre-sulphurization, similar to those described in patents U.S. 4530917, 4719195 and in the application for French patent 92/04051. Catalysts "precultural" thus, to obtain a metallic phase oxysulfide type. In fact, the color of these catalysts goes from blue to dark gray. On the other hand, FASH spectra show that the oxidation state of molybdenum is still essentially + 6, even if the main modification is evaluated with respect to the spectrum of recently cooked (fresh) catalyst. Catalytic activity of catalysts B and C are close.

Catalyst D, sulphonated just using sulfur remains gray, he gives considerable isotherm in the DSC under the action of hydrogen and has a weak catalytic activity.

Catalysts E, F, G according to the invention of the black color did not give any signal ectothermy in the DSC under the action of hydrogen (which makes sense because they are already activated under the action of hydrogen according to the method of the invention). They have spectra FASH characteristic of MoS2with the oxidation state 4+. Catalytic activity the person prior art,

Catalyst H homologous to catalyst E, which, however, are not subjected to oxidizing passivation clearly black and contains Mo4+. However, its catalytic activity is slightly weaker than that of its homologue H that shows the benefit of staging the passivation process.

1. Method for pretreatment of the catalyst in the hydrocarbon processing "ex situ" (out of reactor), namely, that in the catalytic mass is injected sulfureuse agent, process the catalyst with hydrogen at a temperature of from 150 to 700C and provide passivation of the catalyst.

2. The method according to p. 1, namely, that in the catalytic mass is injected at least one sulfureuse agent in the presence of at least one solvent and/or at least one component containing carbon due olefinic type at a temperature of from 0 to 200C, processing sulfonated catalyst conduct pure or diluted hydrogen passivation is carried out by purging the catalyst with air or oxygen-containing gas.

3. The method according to one of the p. 1 or 2, namely, that impose sulfureuse agent at a temperature of from 30 to 200C in the presence minisip, this is followed by a heat treatment "ex situ" catalyst in the absence of the hydrogen treated catalyst pure or diluted with hydrogen, cooling the catalyst to room temperature, followed by exposure to a stream of inert gas, and the purging of the catalyst is carried out first by oxygen, diluted to a concentration below about 10 vol.%, and then the air.

4. The method according to p. 1, namely, that the first stage of processing sulfurous agent and the hydrogen are at the same time.

5. The method according to any of paragraphs. 1-4, namely, that sulfureuse agent is chosen in the group consisting of elemental sulfur, organic polysulfides, hydrogen sulfide, mercaptans, carbon disulfide, sulfides, disulfides, thiophene compounds.

6. The method according to p. 5, namely, that sulfureuse agent is chosen in the group consisting of elemental sulfur, organic polysulfides, dimethyl sulfide and dimethyl disulfide.

7. The method according to any of paragraphs. 2-6, consists in the fact that the solvent is white spirit.

8. The method according to any of paragraphs. 2-6, namely, that component is an olefinic hydrocarbon, in particular, derived from the fatty acids of the oil.


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