Hydrogenation catalyst and preparation method thereof

Technical Field

The invention relates to a hydrogenation catalyst and preparation method thereof, in particular to a heavy oil hydrotreating hydrogenation catalyst and preparation method thereof.

Background Art

With the world's heavy crude oil, and the worsening of trend poor electron particle materialization , residual oil hydrogenation technology is widely concerned, for the inferior residual oil for deep processing not only is favorable for improving the utilization rate of the crude oil, the trend relieve the energy supply, at the same time also able to reduce environmental pollution, realize high efficient and clean the use of the energy. Compared with the distillate oil, in addition to heavy oil having a sulfur, nitrogen and other impurities, also contains a relatively high proportion of Ni, V and metal impurities such as asphaltenes, these impurities on the surface of the catalyst can easily lead to deposition of the device in operation the rise in pressure drop in the process is forced to shut down. Therefore in the low quality residual oil hydroprocessing catalyst in the process with the metal of the series will be directly affected by the operating period of the catalyst. The catalyst has the ability to directly depend on metal of the pore structure of the catalyst, high pore volume, large-pore catalyst because of having good performance and the proliferation of metal of excellent ability of a catalyst has been the main objective of the development.

Chinese Patent CN1054393C discloses a residual oil hydrogenation catalyst, is alumina carrier load and/or group VIII to group VIB metal component, carrier the pore volume is 0.8-1.2 ml/g, a pore size of a 15.0-20.0 nanometer, specific surface is 110-200 m²/g, the preparation method is the added pseudo thinolite physical and chemical bearizing agent, molding and drying to obtain the carrier after roasting, spraying on the active component to carrier. CN1055877C of China Patent discloses a large-pore alumina carrier, the alumina carrier of the pore volume is 0.80-1.20 milliliter/g, can be several hole diameter of 15.0-20.0 nanometer, the specific surface area is 110-200m²/g, the preparation method of the alumina carrier as the added pseudo thinolite physical and chemical bearizing agent, after molding and drying 840-1000 the roasting under [...] 1-5 hours.

The proceeds of the prior art alumina carrier has residual oil hydrotransforming gao Kongrong , the technical characteristics of large aperture, however, with the metal content of 150 PPM residual oil of the above, the prior art the aperture of the of the catalyst is still small, because of the presence of the diffusion resistance of the deposited metal impurities catalyst orifice, causes the catalyst to let metal capacity has been is not given full play to fast inactiviting, therefore effectively increase the catalyst pore oil hydrogenation catalyst is the key.

Content of the invention

The purpose of this invention is to, in view of the prior art is unable to adapt to residual oil hydrotreating catalyst to the high metal requirements for hydrogenation of inferior residual oil, provided with a large aperture, high pore volume heavy oil hydrogenation treatment hydrogenation catalytic solution of the alumina carrier.

The invention provides a hydrogenation catalyst, the catalyst comprises an alumina carrier and at least one member selected from group VIII and at least one selected from the group VIB metal, wherein, the pore volume of the alumina carrier is 0.6-1.2 ml/g, specific surface is 80-200 m²/grams, can be several-hole diameter is 25-35 nanometer, aluminum oxide carrier has distributed following hole the: diameter of less than 20 nanometer hole of the whole volume of the pore volume is less than 50%.

The present invention provides a method for preparing a hydrogenation catalyst, the method including forming the alumina precursor, drying, roasting, selected from at least one group VIII metal and at least one selected from the group VIB metal, wherein, of said alumina precursor pore volume is 0.8-1.5 ml/g, can be several-hole diameter is 8-40nm, the roasting conditions are, in 800-1200 the temperature of the roasting under [...] 1-6 hours.

The present invention provides a hydrogenation catalyst alumina carrier has a larger hole diameter of the, catalyst metal venturi demetalizating of hydrogenation of improved performance. From the embodiments of the present invention can be seen, the present invention provides catalysts in operation 200 and 800 hours later, is obviously higher than the proportion degold is rate.

Mode of execution

In accordance with the present invention the hydrogenation catalyst, the catalyst comprises an alumina carrier and at least one member selected from group VIII and at least one selected from the group VIB metal, wherein, the pore volume of the alumina carrier is 0.6-1.2 ml/g, specific surface is 80-200 m²/grams, can be several-hole diameter is 25-35 nanometer, aluminum oxide carrier has distributed following hole the: diameter of less than 20 nanometer hole of the whole volume of the pore volume is less than 50%.

Preferably, the pore volume of the alumina carrier to 0.7-1.0 ml/g, specific surface is 90-180 m 2/g, can be several-hole diameter is 26-30 nanometer, aluminum oxide carrier has distributed following hole the: diameter of less than 20 nano hole of the total volume of pores with a pore volume 25-45%.

The catalyst according to the present invention, the catalyst comprises the present invention provides aluminum oxide carrier and at least one member selected from group VIII and at least one selected from the group VIB metal. Preferably, the group VIII metal component is a cobalt and/or nickel, group VIB metal component molybdenum and/or tungsten, with a catalyst to oxide counts and for reference, the group VIII metal component content is preferably 0.3-8 weight %, further preferably 0.5-5 weight %, the group VIB metal component content is preferably 0.5-15 weight %, further preferably 3-10 weight %. Based on the total weight of the catalyst, the content of the carrier is preferably 80-98 weight %, further preferably 85-96.5%.

The present invention provides a method for preparing a hydrogenation catalyst, the method including forming the alumina precursor, drying, roasting, selected from at least one group VIII metal and at least one selected from the group VIB metal, wherein, of said alumina precursor pore volume is 0.8-1.5 ml/g, can be several-hole diameter is 8-40nm, the roasting conditions are, in 800-1200 the temperature of the roasting under [...] 1-6 hours.

Under preferred conditions, the baking conditions are, in 900-1100 the temperature of the roasting under [...] 2-4 hours.

The preferred precursor of alumina is hydrated alumina. Hydrated alumina is preferably samizu alumina, alumina and amorphous aluminum hydroxide a water in one or several kinds of. According to the present invention, meets the requirements can be precursor of alumina by commercially-available.

In accordance with the method provided by the invention, the shaping can be carried out according to the conventional method, such as sheeting, rolling ball, such as extrusion method can. When, for example, when the extruder, the mixture can be the right amount of water mixing, and adding an amount of solvent, help pushes the medicinal preparation , then extrusion molding.

According to the present invention, the kind of the solvent and helps pushes the medicinal preparation no special restrictions and consumption, the known technical personnel in the field, such as the solvent can be a nitric acid, acetic acid and citric acid in one or more of; the helps pushes the medicinal preparationsesbania powder , cellulose in one or several kinds of. The solvent and helps pushes the medicinal preparation can be through commercially-available.

The drying is of a conventional method, is known by the technical personnel in the field, such as in utility 120 to maintain the temperature of the [...] under 4 hours.

Under the condition of further preferably, the alumina precursor can be of several-hole diameter is 8 nanometer -20 nanometer, in the conditions of the calcination the 1000 [...] -1200 the temperature of the roasting under [...]. The alumina precursor can be of several-hole diameter is greater than 20 nanometer to 40 nanometer, the conditions for the baking of the 800 [...] above to the less than 1000 the temperature of the roasting under [...]. Although the baking temperature can be changed in a large range, but in the preferred conditions conducive to further roasting under the alumina carrier pore distribution control in a preferred range.

The carrier is introduced to the at least one selected from the group VIII metal and at least one selected from the group VIB metal method is known by the technical personnel in the field, it is generally sufficient to turn selected from the selected from the group VIB and group VIII metal component deposited on the carrier, by containing the compound of group VIII and group VIB metal component of the metal component of the said carrier is impregnated with a solution of compound, with oxide counts and by catalyst as a reference, the amount of each component in the catalyst of group VIII metal component content is preferably 0.3-8 weight %, further preferably 0.5-5 weight %, the group VIB metal component content is preferably 0.5-15 weight %, further preferably 3-10 weight %.

The group VIB compound is selected from the metal component of the soluble compounds of them in one or several kinds of, such as molybdenum oxide, molybdate, in para-molybdic acid salt of one or several, preferably wherein the molybdenum oxide, ammonium molybdate, ammonium paramolybdate by reclaimed material; tungstate, the tungstate, ethyl bias tungstate one or several, preferably the ammonium metatungstate, ethyl ammonium metatungstate.

The compound of the group VIII metal component selected from the group consisting of soluble compounds of them in one or several kinds, such as cobalt nitrate, cobalt acetate, basic cobalt carbonate, cobalt chloride and cobalt in soluble complexes of one or several, preferably cobalt nitrate, basic cobalt carbonate; nickel nitrate, nickel acetate, basic nickel carbonate, nickel and nickel chloride in soluble complexes of one or several, preferably nickel nitrate, basic nickel carbonate.

The present invention provides aluminum oxide carrier and catalyst is particularly suitable for the high metal inferior residual oil is hydroprocessed raw materials such as the use of.

The following examples will further illustrate this invention.

Embodiment 1-4 of the invention provides a large aperture, high pore volume alumina carrier and its preparation method, the nature of the raw materials used are shown in table 1.

Embodiment 1

The 300 the gram plans thin water aluminum stone dry powder (the Changling catalyst factory production PB110) and 10 grams of sesbania powder uniformly mixed, the mixture at room temperature with 360 ml concentration is 1% nitric acid aqueous solution, mix, in a double-screw extruder as the kneading machine, does not continue to be, pressed into ф 1.5 mm trefoiled section, the wet section 120 the drying [...] 4 hours later, for 1000 the roasting [...] 3 hours, to obtain carrier Z1. Measuring Z1 specific surface, pore volume and pore size distribution, the results shown in table 2.

Carrier specific surface, the pore volume and pore size distribution measuring BET low-temperature nitrogen adsorption method.

Embodiment 2

The 300 the gram plans thin water aluminum stone dry powder (the Changling catalyst factory production PB120) and 10 grams of mixed evenly sesbania powder , adding 360 ml concentration is 1% nitric acid aqueous solution, mix, in a double-screw extruder as the kneading machine, does not continue to be, pressed into ф 1.1 mm the butterfly-shaped section, the wet section 120 the drying [...] 2 hours later, for the 950 roasting [...] 2 hours to obtain carrier Z3. In accordance with embodiment 1 of the method to determine the same as Z3 specific surface, pore volume and pore size distribution, a result as shown in table 2 is shown.

Embodiment 3

The 300 grams of aluminum hydroxide powder (Shanxi aluminum factory production) and 10 grams of mixed evenly sesbania powder , adding 360 ml concentration is 3% acetic acid aqueous solution, mix, in a double-screw extruder as the kneading machine, does not continue to be, pressed into ф 1.5 mm the butterfly-shaped section, the wet section 120 the drying [...] 3 hours later, in 1050 the roasting [...] 2 hours to obtain carrier Z4. In accordance with embodiment 1 of the method to determine the same as Z4 specific surface, pore volume and pore size distribution, a result as shown in table 2 is shown.

Embodiment 4

The 150 the gram plans thin water aluminum stone dry powder (the Changling catalyst factory production PB110), 150 grams of aluminum hydroxide powder (Shanxi aluminum factory production) and 10 grams of sesbania powder mix, add 360 ml concentration is 1% nitric acid aqueous solution, mix, in a double-screw extruder as the kneading machine, does not continue to be, pressed into ф 1.1 mm the butterfly-shaped section, the wet section 120 the drying [...] 2 hours later, for 1000 the roasting [...] 3 hours to obtain carrier Z5. In accordance with embodiment 1 of the method to determine the same Z5 specific surface, pore volume and pore size distribution, a result as shown in table 2 is shown.

The proportion 1

The 300 the gram plans thin water aluminum stone dry powder (the Changling catalyst factory production PB80), and 10 grams of sesbania powder uniformly mixed, the mixture at room temperature with 300 ml concentration is 1% nitric acid aqueous solution, mix, in a double-screw extruder as the kneading machine, does not continue to be, pressed into ф 1.5 mm trefoiled section, the wet section 120 the drying [...] 4 hours later, the 780 the roasting [...] 3 hours, to obtain carrier DZ1. In accordance with embodiment 1 of the method to determine the same Z5 specific surface, pore volume and pore size distribution, a result as shown in table 2 is shown.

Table 1

Table 2

Embodiment 5-8 note the catalyst provided by the present invention and method for preparing the same.

Embodiment 5

Taking example 1 preparation of carrier Z1200 g, using 500 ml containing MoO₃   60 grams/liter, NiO 15 g/L of ammonium molybdate and nickel nitrate impregnated with a mixed solution of 1 hour, filtering after the 120 [...] drying 2 hours, 500 the roasting [...] 4 hours, to obtain the catalyst C1. Based on the total weight of the catalyst, measured by X-ray fluorescence spectroscope catalyst C1 in the content of molybdenum oxide and nickel oxide, determination results as shown in table 3 is shown. (All the Rigaku electric industrial Corporation 3271-shaped X-ray fluorescence spectroscope , the specific method see RIPP133-90 petroleum chemical analysis method)

Embodiment 6

Taking embodiment 2 the prepared carrier Z2200 g, with 220 ml containing MoO₃ 90 grams/liter, NiO   20 g/L of ammonium molybdate and nickel nitrate impregnated with a mixed solution of 2 hours, for the 120 [...] drying 2 hours, 550 the roasting [...] 2 hours, to obtain the catalyst C2. With the embodiment in accordance with the 5 measured in the same manner as catalyst C2 in the content of molybdenum oxide and nickel oxide, results as shown in table 3 is shown.

Embodiment 7

The 200 grams of embodiment 3 the prepared carrier Z3, with 500 ml containing MoO₃ 70 grams/liter, NiO 5 grams/liter, CoO   15 g/L of ammonium molybdate, and cobalt nitrate ethyl impregnated with a mixed solution of 1 hour, filtering after the 120 [...] drying 2 hours, 450 the roasting [...] 4 hours, to obtain the catalyst C3. With the embodiment in accordance with the 5 measured in the same manner as catalyst C3 in the molybdenum oxide, the content of nickel oxide and cobalt oxide, results as shown in table 3 is shown.

Embodiment 8

Taking example 4 preparation of carrier Z4200 g, using 500 ml containing MoO₃ 70 grams/liter, CoO   15 g/L of molybdic acid sour ammonium and cobalt nitrate impregnated with a mixed solution of 1 hour, filtering after the 120 [...] drying 2 hours, 480 the roasting [...] 4 hours, to obtain the catalyst C4. With the embodiment in accordance with the 5 measured in the same manner as catalyst C4 in the content of molybdenum oxide and cobalt oxide, results as shown in table 3 is shown.

The ratio 2

Taking 200 grams the proportion 1 DZ1 preparation of the carrier, with 500 ml containing MoO₃   80 grams/liter, NiO 20 g/L of ammonium molybdate and nickel nitrate impregnated with a mixed solution of 1 hour, filtering after the 120 [...] drying 2 hours, 500 the roasting [...] 2 hours, to obtain the catalyst DC1. With the embodiment in accordance with the 5 measured in the same manner as catalyst DC1 in the content of molybdenum oxide and nickel oxide, results as shown in table 3 is shown.

Table 3

Embodiment 9-12

Embodiment 9-12 of the catalyst provided by the present invention by hydrogenation processing performance.

In nickel content is 50 PPM, vanadium content is 140 PPM, a sulfur content of 3.0%, residual carbon is 12% of the atmospheric pressure residual oil as raw material, in 100 ml of small fixed bed reactor the catalyst evaluation.

The catalyst respectively C1-5 is crushed into the diameter 2-3 mm particle, the catalyst filling 100 ml. The reaction condition is the: reaction temperature the 380 [...] , hydrogen partial pressure of 14 MPa, the liquid hourly space velocity of 0.5 hours^-1, hydrogen/oil volume ratio of 1000, reaction 200 hour and 800 hours after each of the sampling analysis, using inductively coupled plasma emission spectrometer measuring (ICP-AES) in the oil after processing the total content of nickel and vanadium. (The instrument used for the United States to PE Company PE-5300 type plasma quantometer , the specific method see RIPP124-90 petroleum chemical analysis method)

In accordance with the following formula calculates the total removal rate of nickel and vanadium:

is rate degold of of each catalyst are shown in table 4.

The proportional 3

With the embodiment in accordance with the 9-12 DC1 same method of evaluation of the catalyst performance of removing metal impurities, the results shown in table 4.

Table 4

The table 4 results can see that, in the low quality the residual oil hydrogenation in the process of the catalyst provided by the present invention and the stability of activity demetalization activity is obviously superior to the existing catalyst, that the catalyst of the invention is more suitable for high metal in the processing of inferior residual oil.