Method for hydrocracking hydrocarbon feedstocks using a catalyst comprising a zeolite and an amorphous mesoporous alumina

Patent metadata

Field	Value
Publication number	US-10723960-B2
Application number	US-201616060069-A
Country	US
Kind code	B2
Filing date	Nov 16, 2016
Priority date	Dec 8, 2015
Publication date	Jul 28, 2020
Grant date	Jul 28, 2020

Abstract

The present invention describes a process for hydrocracking at least one hydrocarbon feed in which at least 50% by weight of the compounds have an initial boiling point of more than 300° C. and a final boiling point of less than 540° C. using at least one catalyst comprising at least one metal from group VIB and/or at least one metal from group VIII of the periodic classification of the elements and a support comprising at least one zeolite containing at least one series of channels the opening of which is defined by a ring containing 12 oxygen atoms (12MR), and at least one binder, said support being prepared from a highly dispersible alumina gel, said hydrocracking process being operated at a temperature in the range 200° C. to 480° C., at a total pressure in the range 1 MPa to 25 MPa, with a ratio of the volume of hydrogen to the volume of hydrocarbon feed in the range 80 to 5000 litres per litre and with an hourly space velocity (HSV), defined as the ratio of the volume flow rate of liquid hydrocarbon feed to the volume of catalyst charged into the reactor, in the range 0.1 to 50 h−1.

First claim

The invention claimed is:

1. A process for hydrocracking at least one hydrocarbon feed in which at least 50% by weight of the compounds have an initial boiling point of more than 300° C. and a final boiling point of less than 540° C., at a temperature in the range 200° C. to 480° C., at a total pressure in the range 1 MPa to 25 MPa, with a ratio of the volume of hydrogen to the volume of hydrocarbon feed in the range 80 to 5000 litres per litre and with an hourly space velocity (HSV), defined as the ratio of the volume flow rate of liquid hydrocarbon feed to the volume of catalyst charged into the reactor, in the range 0.1 to 50 h −1 , said process using at least one catalyst comprising at least one metal from group VIE and/or at least one metal from group VIII of the periodic classification and a support comprising at least one zeolite containing at least one series of channels the opening of which is defined by a ring containing 12 oxygen atoms (12MR), and at least one binder comprising at least one amorphous mesoporous alumina,
said support comprising at least said zeolite and at least said binder being prepared in accordance with at least the following steps:
a) a first step for alumina precipitation, in an aqueous reaction medium, of at least one basic precursor selected from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide and at least one acidic precursor selected from aluminium sulphate, aluminium chloride, aluminium nitrate, sulphuric acid, hydrochloric acid and nitric acid, in which at least one of the basic or acidic precursors comprises aluminium, the relative flow rate of the acidic and basic precursors being selected in a manner such as to obtain a pH of the reaction medium in the range 8.5 to 10.5 and the flow rate of the acidic and basic precursor or precursors containing aluminium being adjusted in a manner such as to obtain a percentage completion of said first precipitation step in the range of 45% to 90%, the percentage completion being defined as being the proportion of alumina formed during said first precipitation step with respect to the total quantity of alumina formed at the end of step
c) of the preparation process, said step being operated at a temperature in the range of 20° C. to 40° C., and for a period in the range of 2 minutes to 30 minutes, to obtain a first suspension,
a1) a step for heating the first suspension obtained at the end of step a) and carried out between step a) and step a′), at a temperature between 20° C. to 90° C. for a period between 7 to 45 minutes,
a′) a second step for precipitation of the heated first suspension obtained at the end of the heating step a1), comprising adding to said heated first suspension at least one basic precursor selected from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide, and at least one acidic precursor selected from aluminium sulphate, aluminium chloride, aluminium nitrate, sulphuric acid, hydrochloric acid and nitric acid, in which at least one of the basic or acidic precursors comprises aluminium, the relative flow rate of the acidic and basic precursors being selected in a manner such as to obtain a pH of the reaction medium in the range 8.5 to 10.5 and the flow rate of the acidic and basic precursor or precursors containing aluminium being adjusted in a manner such as to obtain a percentage completion of the second precipitation step in the range of 10 to 55%, said percentage completion of the second precipitation step being defined as being the proportion of alumina formed during said second precipitation step with respect to the total quantity of alumina formed at the end of the precipitation steps, said second precipitation step being operated at a temperature between 40° C. and 90° C., and for a period between 2 minutes and 50 minutes, to obtain a second suspension,
a2) a second step for heating the second suspension obtained at the end of said second precipitation step a′) to a temperature between 50° C. and 95° C.,
b) a step for hydrothermal treatment of the heated second suspension obtained at the end of the second heating step a2), by heating to a temperature in the range 50° C. to 200° C. for a period in the range 30 minutes to 5 hours in order to obtain an alumina gel,
c) a step for filtration of the suspension obtained at the end of the hydrothermal treatment step b), followed by at least one step for washing the alumina gel obtained,
d) a step for drying the alumina gel obtained at the end of step c) in order to obtain a powder,
e) a step for shaping the powder obtained at the end of step d) as a mixture with at least said zeolite containing at least one series of channels the opening of which is defined by a ring of 12 oxygen atoms (12MR), in order to obtain a green material,
f) a step for calcining the green material obtained at the end of step e) at a temperature in the range 500° C. to 1000° C., in the presence or absence of a stream of air containing up to 60% by volume of water.

2. The process as claimed in claim 1 , in which the metal from group VIB is selected from the group formed by tungsten and molybdenum, used alone or as a mixture.

3. The process as claimed in claim 1 , in which the metal from group VIII is selected from the group formed by cobalt and nickel, used alone or as a mixture.

4. The process as claimed in claim 1 , in which said catalyst comprises at least one metal from group VIB in combination with at least one non-noble metal from group VIII, the content of the metal from group VIB being in the range, as the oxide equivalent, 5% to 40% by weight with respect to the total weight of said catalyst and the content of non-noble metal from group VIII being in the range, as the oxide equivalent, 0.5% to 10% by weight with respect to the total weight of said catalyst.

5. The process as claimed in claim 1 , in which the zeolite used in the catalyst support is selected from zeolites with structure type FAU, BEA, ISV, IWR, IWW, MEI or UWY, used alone or as a mixture.

6. The process as claimed in claim 5 , in which the zeolite is selected from zeolites with structure type FAU and BEA, used alone or as a mixture.

7. The process as claimed in claim 6 , in which the zeolite is selected from Y zeolite and beta zeolite, used alone or as a mixture.

8. The process as claimed in claim 1 , in which the percentage completion of said first precipitation step a) is in the range 50% to 85%.

9. The process as claimed in claim 1 , in which said at least one hydrocarbon feed is selected from light gas oils obtained from a catalytic cracking unit, atmospheric distillates, vacuum distillates, feeds from units for the extraction of aromatics from lubricating base oils or obtained from solvent dewaxing lubricating base oils, the distillates from processes for fixed bed or ebullated bed desulphurization or hydroconversion of atmospheric residues and/or vacuum residues and/or deasphalted oils, deasphalted oils and paraffins obtained from the Fischer-Tropsch process, used alone or as a mixture.

Assignees

• Ifp Energies Now

Inventors

• Boualleg Malika
• Daudin Antoine
• Guillon Emmanuelle

Classifications

• C01F7/141

  from aqueous aluminate solutions by neutralisation with an acidic agent · CPC title

• C10G2300/1074

  Vacuum distillates · CPC title

• B01J21/04

  Alumina · CPC title

• B01J37/0045

  Drying a slurry, e.g. spray drying · CPC title

• B01J29/084

  Y-type faujasite · CPC title