# US 8,541,636 B2 · Process for hydrotreating a diesel fuel feedstock, hydrotreating unit for implementing said process, and corresponding hydrorefining unit

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- Number: US 8,541,636 B2
- Document ID: US8541636B2
- Status: Granted
- Kind: B2
- Application number: 12/526,601
- Filed: 2008-02-12
- Published: 2010-02-18
- Granted: 2013-09-24
- Earliest claimed: 2007-02-27
- Assignees: Total Raffinage Marketing
- Applicants: César Vergel
- Inventors: César Vergel
- Web page: https://patentgrep.com/patent/US8541636B2

## CPC

- C10G 45/58: to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins (C10G32/00 takes precedence; improving or increasing the octane number or aromatic content of naphtha C10G35/00)
- B01J 8/0488: {the beds being placed in separate reactors}
- C10G 3/45: {containing iron group metals or compounds thereof}
- C10G 3/46: {in combination with chromium, molybdenum, tungsten metals or compounds thereof}
- C10G 3/47: {containing platinum group metals or compounds thereof}
- C10G 3/48: {further characterised by the catalyst support}
- C10G 3/49: {containing crystalline aluminosilicates, e.g. molecular sieves}
- C10G 3/50: {in the presence of hydrogen, hydrogen donors or hydrogen generating compounds}
- C10G 3/54: {characterised by the catalytic bed}
- C10G 3/60: {Controlling or regulating the processes}
- C10G 49/002: {Apparatus for fixed bed hydrotreatment processes}
- C10G 65/04: including only refining steps
- C11C 3/123: {using catalysts based principally on nickel or derivates}
- C11C 3/126: {using catalysts based principally on other metals or derivates}
- B01J 2219/00006: Large-scale industrial plants
- C10G 2300/1014: of vegetal origin
- C10G 2300/1018: of animal origin
- C10G 2300/1022: Fischer-Tropsch products
- C10G 2300/1074: Vacuum distillates
- C10G 2300/207: Acid gases, e.g. H2S, COS, SO2, HCN
- C10G 2300/4018: Spatial velocity, e.g. LHSV, WHSV
- C10G 2300/805: Water
- Y02E 50/10: Biofuels, e.g. bio-diesel
- Y02P 30/20: using bio-feedstock
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C11C: FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The invention relates to a method for the catalytic hydrotreatment of a load based on a diesel fuel oil and a biological load based on plant oils and/or animal fats in a hydrotreatment unit. The invention is characterized in that the hydrotreatment unit comprises at least one hydrotreatment reactor operating on a countercurrent. The invention also relates to a hydrotreatment unit for implementing said method, and a corresponding hydrorefining unit.

## Claims

### Claim 1

Process for the catalytic hydrotreating of a feedstock of oil origin, of diesel fuel type, and of a feedstock of biologicial origin based on vegetable oils and/or animal fats, comprising hydrotreating said feedstocks in a hydrotreating unit, characterized in that said hydrotreating unit comprises at least one fixed-bed hydrotreating reactor operating countercurrently with hydrogen.

### Claim 2 (depends on 1)

Catalytic hydrotreating process according to claim 1, characterized in that the hydrotreating unit comprises a single reactor operating countercurrently into which the feedstocks of oil and biological origin are injected.

### Claim 3 (depends on 1)

Catalytic hydrotreating process according to claim 1, characterized in that the hydrotreating unit comprises two separate reactors, a first reactor operating cocurrently and a second reactor operating countercurrently that receives the liquid effluent exiting the first reactor, and in that the feedstock of oil origin is injected into the first, cocurrent reactor, and the feedstock of biological origin is injected into the first, cocurrent and/or into the second, countercurrent reactor as a mixture with the liquid effluent exiting the first reactor.

### Claim 4 (depends on 1)

Catalytic hydrotreating process according to claim 1, in which the feedstock of oil origin, of diesel fuel type, is chosen from diesel fuel cuts resulting from the distillation of a crude oil and/or of a synthetic crude derived from the treatment of oil shales or of heavy and extra-heavy crude oils or of the effluent from the Fischer-Tropsch process.

### Claim 5 (depends on 1)

Catalytic hydrotreating process according to claim 1, in which the level of the feedstock of biological origin based on vegetable oils and/or animal fats is up to 30% by weight.

### Claim 6 (depends on 5)

Catalytic hydrotreating process according to claim 5, in which the level of the feedstock of biological origin based on vegetable oils and/or animal fats is less than or equal to 15% by weight.

### Claim 7 (depends on 1)

Catalytic hydrotreating process according to claim 1, in which the vegetable oils contained in the feedstock of biological origin are chosen from palm oil, soya bean oil, rapeseed oil, sunflower oil, linseed oil, rice bran oil, maize oil, olive oil, castor oil, sesame oil, pine oil, peanut oil, palm kernel oil, coconut oil, babassu oil, oil derived from algae, or a mixture of two or more of these oils.

### Claim 8 (depends on 7)

Catalytic hydrotreating process according to claim 7, characterized in that the vegetable oils comprise palm oil.

### Claim 9 (depends on 1)

Catalytic hydrotreating process according to claim 1, in which the feedstock of biological origin is injected into a catalytic region comprising a first metal-trapping catalyst layer.

### Claim 10 (depends on 1)

Catalytic hydrotreating process according to claim 1, in which the amount of hydrogen introduced into the countercurrent reactor is from 50 to 2000 Normal liters of H2 per liter of feedstock.

### Claim 11 (depends on 1)

Catalytic hydrotreating process according to claim 1, in which the feedstock treatment temperature in the countercurrent reactor is from 250 to 420° C.

### Claim 12 (depends on 1)

Catalytic hydrotreating process according to claim 1, in which the feedstock is treated at a pressure of 25 to 150 bar.

### Claim 13 (depends on 1)

Catalytic hydrotreating process according to claim 1, in which the HSV of the feedstock in the countercurrent reactor is from 0.3 to 10.

### Claim 14 (depends on 1)

Catalytic hydrotreating process according to claim 1, in which the feedstock of biological origin passes through at least one catalyst bed in the hydrotreating unit, the catalyst bed containing at least one catalyst based on metal oxides chosen from the oxides of group VI-B metals, and group VIII-B metals and/or noble metals, supported on a support chosen from alumina, silica, silica-alumina, zeolite, ferrierite, phosphated alumina, phosphated silica-alumina, mordenite or mazite.

### Claim 15 (depends on 14)

Catalytic hydrotreating process according to claim 14, wherein the group VI-B metals are selected from Mo and W, the group VIII-B metals are selected from Co, Ni, Ru and Rh, and the noble metals are selected from Pt and Pd.

### Claim 16 (depends on 1)

Catalytic hydrotreating process according to claim 1, in which the feedstock of biological origin introduced into the hydrotreating unit is treated over at least one catalyst bed containing, at least in part, a catalyst with an isomerizing function, based on metal oxides or on oxides of noble metals, on an acidic support selected from amorphous silica-alumina, zeolite, ferrierite, phosphated alumina and phosphated silica-alumina.

### Claim 17 (depends on 16)

Catalytic hydrotreating process according to claim 16, wherein the noble metals are selected from Pt and Pd.

### Claim 18 (depends on 1)

Catalytic hydrotreating process according to claim 1, in which water is injected into the hydrotreating unit in the region for treating the feedstock of biological origin.

### Claim 19 (depends on 1)

Catalytic hydrotreating process according to claim 1, comprising treatment of a recycling gas coming from the hydrotreating unit before its reinjection into said unit, in which an additional treatment of the carbon monoxide present in said recycling gas is carried out.

### Claim 20 (depends on 19)

Catalytic hydrotreating process according to claim 19, in which the carbon monoxide is treated by means of a CO conversion unit using the “CO shift” reaction.

### Claim 21 (depends on 19)

Catalytic hydrotreating process according to claim 19, in which the carbon monoxide CO, and optionally methane CH4, ethane C2H6, and propane C3H8, are separated by means of a PSA treatment unit.

### Claim 22 (depends on 21)

Catalytic hydrotreating process according to claim 21, in which the separated carbon monoxide CO, and optionally the separated methane CH4, ethane C2H6, and propane C3H8, are used in a steam reformer.

### Claim 23 (depends on 1)

Catalytic hydrotreating process according to claim 1, comprising treatment of a recycling gas coming from the hydrotreating unit before its reinjection into said unit, in which, in addition, a treatment is carried out during which the carbon dioxide (CO2) and hydrogen sulphide (H2S) present in said recycling gas are separated and treated.

### Claim 24 (depends on 1)

Catalytic hydrotreating process according to claim 1, in which the exothermicity of the hydrotreating of the feedstock of biological origin is controlled by means of thermal control systems.

### Claim 25 (depends on 1)

Hydrorefining unit comprising at least one catalytic hydrotreating unit in fluid communication with a feedstock of oil origin, of diesel fuel type, and of a feedstock of biological origin configured to implement the process according to claim 1, said hydrotreating unit comprising at least one fixed-bed hydrotreating reactor operating countercurrently, the hydrorefining unit comprising a system configured to treat recycling gases derived from the hydrotreating unit before they are reinjected into said unit, this treatment system comprising a device for separating and treating carbon monoxide so as to remove the carbon monoxide present in said recycling gas.

### Claim 26 (depends on 25)

Hydrorefining unit according to claim 25, characterized in that the hydrotreating unit comprises a single reactor operating countercurrently.

### Claim 27 (depends on 25)

Hydrorefining unit according to claim 25, characterized in that the hydrotreating unit comprises two separate reactors, a first reactor reacting cocurrently and a second reactor operating countercurrently that receives the liquid effluent exiting the first reactor.