# US 9,518,233 B2 · Catalyst for a hydrodgenation dewaxing process and method for manufacturing same

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- Number: US 9,518,233 B2
- Document ID: US9518233B2
- Status: Granted
- Kind: B2
- Application number: 14/306,447
- Filed: 2014-06-17
- Published: 2014-12-18
- Granted: 2016-12-13
- Earliest claimed: 2010-04-14
- Assignees: SK Innovation Co., Ltd.
- Applicants: SK Innovation Co., Ltd.
- Inventors: Tae Jin Kim; Seung Woo Lee; Yoon Kyung Lee; Seung Hoon Oh; Jae Suk Choi
- Web page: https://patentgrep.com/patent/US9518233B2

## CPC

- C10G 47/16: Crystalline alumino-silicate carriers
- B01J 29/72: containing iron group metals, noble metals or copper
- B01J 29/74: Noble metals
- B01J 35/615: {100-500 m2/g}
- C01B 39/48: using at least one organic template directing agent
- C07C 5/2775: {with crystalline alumino-silicates, e.g. molecular sieves}
- C10G 45/62: containing platinum group metals or compounds thereof
- C10G 45/64: containing crystalline alumino-silicates, e.g. molecular sieves
- B01J 35/70: characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00)
- B01J 2229/20: to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
- B01J 2229/42: Addition of matrix or binder particles
- B01J 2235/15: X-ray diffraction
- C07C 9/22: with more than fifteen carbon atoms
- C07C 2523/42: Platinum
- C07C 2523/44: Palladium
- C07C 2523/58: with alkali- or alkaline earth metals or beryllium
- C07C 2529/74: Noble metals
- C10G 2300/4018: Spatial velocity, e.g. LHSV, WHSV
- C10G 2400/02: Gasoline
- C10G 2400/04: Diesel oil
- C10G 2400/10: Lubricating oil
- Y02P 20/52: using catalysts, e.g. selective catalysts
- 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
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The present invention relates to a bifunctional catalyst for a hydrodewaxing process with improved isomerization selectivity, and to a method for manufacturing the same, and more particularly to a bifunctional catalyst and to a method for manufacturing same, which is characterized in that EU-2 zeolite with a controlled degree of phase transformation is used as a catalyst support having an acid site. The EU-2 zeolite, the degree of phase transformation of which is controlled, includes, by controlling synthesis parameters of EU-2, predetermined amounts of materials that are phase-transformed from EU-2 crystals such as cristobalite and quartz. The metal loaded bifunctional catalyst according to the present invention improves selectivity of the isomerization process, rather than a cracking reaction, during a hydroisomerization reaction of n-hexadecane. Therefore, the bifunctional catalyst can be widely used as a catalyst for a dewaxing process such as lubricant base oil and diesel oil.

## Claims

### Claim 1

A hydrodewaxing method of a hydrocarbon raw material, wherein the hydrocarbon raw material is hydrodewaxed in the presence of a catalyst under the reaction conditions of a temperature of 250˜420° C., a hydrogen partial pressure of 1˜200 atm, a liquid hourly space velocity of 0.1˜10 h−1 and a hydrogen treatment rate of 250˜10,000 scf/B, wherein the catalyst comprises
an EU-2 zeolite support having an acid site, the phase transition index (T) thereof, represented by Formula 1 below, being 60≦T<98, and the molar ratio of silica and alumina thereof being 20 to 200; and
a metal composition for hydrogenation loaded in the EU-2 zeolite support, the metal composition including at least one metal selected from the group consisting of group VI metals and group VIII metals,
wherein <Formula 1> T=(TGA weight reduction rate of the synthesized EU-2 sample)/(TGA weight reduction rate of pure EU-2 reference sample)×100 (here, the TGA weight reduction rate of the EU-2 sample is measured under the condition that the sample is heated from 120° C. to 550° C. at a heating rate of 2° C./min and then maintained at 550° C. for 2 hours).

### Claim 2 (depends on 1)

The hydrodewaxing method of a hydrocarbon raw material according to claim 1, wherein the metal composition is palladium or platinum.

### Claim 3 (depends on 1)

The hydrodewaxing method of a hydrocarbon raw material according to claim 1, wherein the catalyst further comprises at least one co-catalyst selected from the group consisting of group I metals and group II metals.

### Claim 4 (depends on 3)

The hydrodewaxing method of a hydrocarbon raw material according to claim 3, wherein each of the group I metals and group II metals is selected from sodium, magnesium and calcium.

### Claim 5

A hydrodewaxing method of a hydrocarbon raw material, wherein the hydrocarbon raw material is hydrodewaxed in the presence of a catalyst under the reaction conditions of a temperature of 250˜420° C., a hydrogen partial pressure of 1˜200 atm, a liquid hourly space velocity of 0.1˜10 h−1 and a hydrogen treatment rate of 250˜10,000 scf/B, wherein the catalyst is prepared by the steps of:
(a) preparing an EU-2 zeolite support, the degree of phase transition of which is controlled such that a phase transition index (T) thereof is 60≦T<98;
(b) loading a active metal composition on the EU-2 zeolite support for hydrogenation, the metal composition including at least one metal selected from the group consisting of group VI metals and group VIII metals; and
(c) drying and calcinating the EU-2 zeolite support loaded with the metal composition, wherein T=(TGA weight reduction rate of the synthesized EU-2 sample)/(TGA weight reduction rate of pure EU-2 reference sample)×100 (here, the TGA weight reduction rate of the EU-2 sample is measured under the condition that the sample is heated from 120° C. to 550° C. at a heating rate of 2° C./min and then maintained at 550° C. for 2 hours).

### Claim 6 (depends on 5)

The hydrodewaxing method of a hydrocarbon raw material according to claim 5, wherein the step (a) comprises the steps of: (i) mixing a template material with an aqueous alkali solution including a silica raw material and an alumina raw material; (ii) reacting the mixture at a temperature of 50˜250° C. to obtain an EU-2 zeolite, the degree of phase transition of which is controlled such that the phase transition index (T) thereof is 60≦T<98; and (iii) washing and drying the EU-2 zeolite.

### Claim 7 (depends on 6)

The hydrodewaxing method of a hydrocarbon raw material according to claim 6, wherein the template material is at least one member selected from the group consisting of alkyl amines, tetramethyl ammonium compounds and di-quaternary ammonium compounds.

### Claim 8 (depends on 5)

The hydrodewaxing method of a hydrocarbon raw material according to claim 5, wherein the step (b) further comprises the step of adding at least one co-catalyst selected from the group consisting of group I metals and group II metals.

### Claim 9 (depends on 8)

The hydrodewaxing method of a hydrocarbon raw material according to claim 8, wherein each of the group I metals and group II metals is selected from sodium, magnesium and calcium.