US20010021688A1 - Catalyst for steam cracking reactions and related preparation process - Google Patents

Catalyst for steam cracking reactions and related preparation process Download PDF

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Publication number
US20010021688A1
US20010021688A1 US09/736,306 US73630600A US2001021688A1 US 20010021688 A1 US20010021688 A1 US 20010021688A1 US 73630600 A US73630600 A US 73630600A US 2001021688 A1 US2001021688 A1 US 2001021688A1
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US
United States
Prior art keywords
catalyst
process according
calcium
steam cracking
aluminum
Prior art date
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Abandoned
Application number
US09/736,306
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English (en)
Inventor
Paolo Pollesel
Caterina Rizzo
Carlo Perego
Renato Paludetto
Gastone Del Piero
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Eni Tecnologie SpA
Enichem SpA
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Enichem SpA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Assigned to ENICHEM S.P.A., ENITECNOLOGIE S.P.A. reassignment ENICHEM S.P.A. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DEL PIERO, GASTONE, PALUDETTO, RENATO, PEREGO, CARLO, POLLESEL, PAOLO, RIZZO, CATERINA
Publication of US20010021688A1 publication Critical patent/US20010021688A1/en
Priority to US10/309,145 priority Critical patent/US6696614B2/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/16—Preparation of alkaline-earth metal aluminates or magnesium aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/164—Calcium aluminates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data

Definitions

  • the present invention relates to a catalyst for steam cracking reactions and the related preparation process.
  • a technology which seems closer to a possible industrial application is the Pyrocat process, set up by Veba Oel and Linde (M. Wyrosteck, M. Rupp, D. Kaufmann, H. Zimmermann, Proc. 15 th World Petroleum Congress, Beijing, Oct. 12-16, 1997).
  • This technology comprises implementation of steam cracking plants without modifying the design of the ovens.
  • the idea is based on coating the inside of the cracking tubes with a solid layer having a catalytic effect and which inhibits the formation of coke, thus prolonging the times between subsequent stoppages for decoking operations.
  • the catalyst is based on Al 2 O 3 /CaO and contains, as gasification promoter, compounds of alkaline metals.
  • the technology however can only be applied to conventional cracking plants, operating with conventional charges.
  • the catalyst for steam cracking reactions object of the present invention, is characterized in that it consists of pure mayenite having the general formula:
  • the polyfunctional organic hydroxyacids can be selected from citric acid, maleic acid, tartaric acid, glycolic acid and lactic acid: citric acid is preferred.
  • the salts containing calcium are preferably selected from calcium acetate and calcium nitrate.
  • Aluminum nitrate is the preferred salt containing aluminum.
  • a further object of the invention relates to the process for the production of light olefins by means of the steam cracking reaction of hydrocarbon charges selected from naphtha, in particular virgin naphtha, kerosene, atmospheric gas oil, vacuum gas oil, alone or mixed with each other, in the presence of a catalyst according to claim 1 , which is effected preferably operating at a temperature ranging from 720 to 800° C., at a pressure ranging from 1.1 to 1.8 absolute Atm and for a contact time ranging from 0.07 to 0.2 sec.
  • This method comprises the use of citric acid or polyfunctional hydroxyacids which have the function of complexing metal salts in aqueous solution. After dehydration of the aqueous solution an amorphous solid precursor is obtained, which, after thermal treatment at a high temperature, produces the desired product.
  • a solution of aluminum nitrate, 378.2 g of Al(NO 3 ) 3 .9H 2 O (1.008 moles) in 470 g of water was first added to a solution of calcium acetate, obtained by dissolving at room temperature 152.2 g of (CH 3 COO) 2 Ca.H 2 O (0.864 moles) in 450 g of H 2 O, followed by a solution of citric acid: 393.1 g (1.872 moles) in 375 g of water.
  • the homogeneous solution obtained was dried by means of a spray-dryer.
  • the desired product 12CaO.7Al 2 O 3 (Mayenite) was obtained in pure form after calcination at 1350° C. for 5 h.
  • a lubricating agent (2 wt % of stearic acid) was added; after tableting, the catalyst was subjected to an additional calcination step.
  • composition of the catalyst obtained was verified by means of X-ray diffractometry, which showed the presence of the single pure 12CaO.7Al 2 O 3 phase.
  • a lubricating agent (2 wt % of stearic acid) was added; after tableting, the catalyst was subjected to an additional calcination step.
  • a solution of aluminum nitrate, 577.7 g of Al(NO 3 ) 3 .9H 2 O (1.540 moles) in 720 g of water was first added to a solution of calcium acetate, obtained by dissolving at room temperature 67.83 g of (CH 3 COO) 2 Ca.H 2 O (0.385 moles) in 200 g of H 2 O, followed by a solution of citric acid: 404.3 g (1.925 moles) in 380 g of water.
  • the homogeneous solution obtained was dried by means of a spray-dryer.
  • the desired product CaO.2Al 2 O 3 was obtained in pure form after calcination at 1350° C. for 5 h.
  • a lubricating agent (2 wt % of stearic acid) was added; after forming, the catalyst was subjected to an additional calcination step.
  • composition of the catalyst obtained was verified by means of X-ray diffractometry, which showed the presence of the single pure CaO.2Al 2 O 3 phase.
  • quartz in granules, or inert material as reference for evaluating the catalyst performances (Example 4: comparative);

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
US09/736,306 1999-12-17 2000-12-15 Catalyst for steam cracking reactions and related preparation process Abandoned US20010021688A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US10/309,145 US6696614B2 (en) 1999-12-17 2002-12-04 Catalyst for steam cracking reactions and related preparation process

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI99A002616 1999-12-17
IT1999MI002616A IT1313698B1 (it) 1999-12-17 1999-12-17 Catalizzatore per reazioni di steam cracking e relativo procedimentodi preparazione.

Related Child Applications (1)

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US10/309,145 Division US6696614B2 (en) 1999-12-17 2002-12-04 Catalyst for steam cracking reactions and related preparation process

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US20010021688A1 true US20010021688A1 (en) 2001-09-13

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US09/736,306 Abandoned US20010021688A1 (en) 1999-12-17 2000-12-15 Catalyst for steam cracking reactions and related preparation process
US10/309,145 Expired - Fee Related US6696614B2 (en) 1999-12-17 2002-12-04 Catalyst for steam cracking reactions and related preparation process

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Country Status (19)

Country Link
US (2) US20010021688A1 (sh)
EP (1) EP1114676B1 (sh)
CN (1) CN1202213C (sh)
AT (1) ATE444806T1 (sh)
BG (1) BG105043A (sh)
CA (1) CA2328040C (sh)
CZ (1) CZ302058B6 (sh)
DE (1) DE60043095D1 (sh)
DK (1) DK1114676T3 (sh)
ES (1) ES2334325T3 (sh)
HR (1) HRP20000871A2 (sh)
HU (1) HUP0004960A3 (sh)
IT (1) IT1313698B1 (sh)
NO (1) NO324157B1 (sh)
PL (1) PL190725B1 (sh)
PT (1) PT1114676E (sh)
SK (1) SK19142000A3 (sh)
TR (1) TR200003749A2 (sh)
YU (1) YU79600A (sh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040192545A1 (en) * 2002-05-16 2004-09-30 Kang Jung Hwa Method for preparing a catalyst for partial oxidation of propylene

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006341223A (ja) * 2005-06-10 2006-12-21 Oxy Japan:Kk 気体状有機化合物の処理装置および処理方法
KR101270191B1 (ko) 2005-08-15 2013-05-31 상하이 리서치 인스티튜트 오브 페트로케미칼 테크놀로지 시노펙 유동상 촉매를 사용하여 촉매 분해에 의하여 에틸렌 및 프로필렌을 제조하는 방법
US9480975B2 (en) 2005-08-15 2016-11-01 China Petroleum & Chemical Corporation Catalyst for catalytic cracking in a fluidized bed
EP1935478A1 (en) * 2006-12-20 2008-06-25 Oxy Japan Corporation Gaseous organic compound disposal system and method
CN101314126B (zh) * 2007-05-31 2011-07-20 中国石油化工股份有限公司 一种蒸汽裂解催化剂及其制备方法和应用
JP5245455B2 (ja) * 2008-02-28 2013-07-24 旭硝子株式会社 マイエナイト型化合物
WO2010041558A1 (ja) * 2008-10-06 2010-04-15 旭硝子株式会社 酸化物の製造方法
CN101974325B (zh) * 2010-10-28 2013-05-15 陕西科技大学 一种镨掺杂七铝酸十二钙光致发光粉体的制备方法
US9573822B2 (en) 2012-08-30 2017-02-21 Tokyo Institute Of Technology Method for producing conductive mayenite compound powder
WO2014045780A1 (ja) 2012-09-20 2014-03-27 国立大学法人東京工業大学 水素生成触媒及び水素の製造法
CN105163851A (zh) 2013-04-29 2015-12-16 沙特基础工业公司 石脑油转化成烯烃的催化方法
CN105294404B (zh) * 2015-09-10 2017-10-24 沈阳化工大学 利用负载型氧化钙除水剂去除苯甲醚中水分的方法
CN109208079B (zh) * 2018-08-22 2020-09-22 武汉大学 一种钙铝石型半导体材料的制备方法
ES2897523B2 (es) 2021-08-10 2022-07-18 Advanced Thermal Devices S L Cátodo basado en el material C12A7:e ''electride'' para la emisión termiónica de electrones y procedimiento para el empleo del mismo
CN114405495A (zh) * 2022-02-16 2022-04-29 华中科技大学 一种介孔钙基催化剂及其制备方法和应用

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NL83582C (sh) * 1952-11-01
US3969542A (en) * 1974-07-12 1976-07-13 Toyo Engineering Corporation Catalysts and methods of making
US4331451A (en) * 1980-02-04 1982-05-25 Mitsui Toatsu Chemicals, Inc. Catalytic gasification
DD243647A1 (de) * 1985-12-02 1987-03-11 Akad Wissenschaften Ddr Katalysator aus einem gesintertem formgegenstand auf calciumaluminatbasis und verfahren zur herstellung
NZ222691A (en) * 1987-12-29 1991-05-28 Nz Government Production of high temperature metal oxide superconductors
DE4400430A1 (de) * 1994-01-10 1995-07-13 Linde Ag Verfahren zum thermokatalytischen Spalten von höhersiedenden Kohlenwasserstoffen und Spaltofen
EP0728831B1 (de) * 1995-02-17 2000-07-12 Linde Aktiengesellschaft Verfahren zum Spalten von Kohlenwasserstoffen und Vorrichtung

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040192545A1 (en) * 2002-05-16 2004-09-30 Kang Jung Hwa Method for preparing a catalyst for partial oxidation of propylene
US7341974B2 (en) 2002-05-16 2008-03-11 Lg Chem, Ltd. Method for preparing a catalyst for partial oxidation of propylene

Also Published As

Publication number Publication date
HRP20000871A2 (en) 2001-06-30
ITMI992616A1 (it) 2001-06-17
DE60043095D1 (de) 2009-11-19
ITMI992616A0 (it) 1999-12-17
HU0004960D0 (sh) 2001-02-28
PL344565A1 (en) 2001-06-18
YU79600A (sh) 2003-04-30
TR200003749A3 (tr) 2001-07-23
EP1114676A2 (en) 2001-07-11
ATE444806T1 (de) 2009-10-15
HUP0004960A3 (en) 2002-04-29
NO20006441L (no) 2001-06-18
CA2328040C (en) 2010-06-08
ES2334325T3 (es) 2010-03-09
US20030109376A1 (en) 2003-06-12
DK1114676T3 (da) 2010-02-15
CZ20004628A3 (cs) 2001-08-15
EP1114676B1 (en) 2009-10-07
EP1114676A3 (en) 2002-02-06
CN1202213C (zh) 2005-05-18
IT1313698B1 (it) 2002-09-09
BG105043A (bg) 2001-11-30
PT1114676E (pt) 2010-01-08
CZ302058B6 (cs) 2010-09-22
HUP0004960A2 (hu) 2001-08-28
PL190725B1 (pl) 2005-12-30
TR200003749A2 (tr) 2001-07-23
NO324157B1 (no) 2007-09-03
SK19142000A3 (sk) 2001-11-06
CN1317546A (zh) 2001-10-17
NO20006441D0 (no) 2000-12-15
CA2328040A1 (en) 2001-06-17
US6696614B2 (en) 2004-02-24

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Owner name: ENICHEM S.P.A., ITALY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:POLLESEL, PAOLO;RIZZO, CATERINA;PEREGO, CARLO;AND OTHERS;REEL/FRAME:011678/0252

Effective date: 20010328

Owner name: ENITECNOLOGIE S.P.A., ITALY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:POLLESEL, PAOLO;RIZZO, CATERINA;PEREGO, CARLO;AND OTHERS;REEL/FRAME:011678/0252

Effective date: 20010328

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