EP3645490A1 - Process for manufacture of ethylene glycol - Google Patents

Process for manufacture of ethylene glycol

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Publication number
EP3645490A1
EP3645490A1 EP17916378.7A EP17916378A EP3645490A1 EP 3645490 A1 EP3645490 A1 EP 3645490A1 EP 17916378 A EP17916378 A EP 17916378A EP 3645490 A1 EP3645490 A1 EP 3645490A1
Authority
EP
European Patent Office
Prior art keywords
process according
catalyst
hydrogen peroxide
ethylene glycol
reaction mixture
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP17916378.7A
Other languages
German (de)
French (fr)
Other versions
EP3645490A4 (en
Inventor
Peng Wu
Xinqing LU
Wenjuan ZHOU
Frédérique DESMEDT
Pierre Dournel
Armin T. LIEBENS
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solvay SA
East China Normal University
Original Assignee
Solvay SA
East China Normal University
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
Application filed by Solvay SA, East China Normal University filed Critical Solvay SA
Publication of EP3645490A1 publication Critical patent/EP3645490A1/en
Publication of EP3645490A4 publication Critical patent/EP3645490A4/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/7088—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/026—After-treatment
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/34—Reaction with organic or organometallic compounds
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/38—Base treatment
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a process for the manufacture of ethylene glycol starting from ethylene (Ee) .
  • Ethylene Glycol (Mono-Ethylene Glycol or MEG) is an important organic chemical raw material mainly used in the production of polyester (more precisely of PET or poly-ethylene-terephthalate) and as antifreeze agent.
  • ethylene glycol production is generally made using a non-catalytic direct hydration method wherein ethylene oxide (EO) and water are reacted generally in a molar ratio of about 1: 20-22 (molar ratio) resulting in an ethylene glycol aqueous solution containing only about 10% (mass fraction) of MEG, the rest being water and by-products like diethylene glycol (DEG) and triethylene glycol (TEG) .
  • EO ethylene oxide
  • DEG diethylene glycol
  • TEG triethylene glycol
  • Increasing the amount of water used for this method can reduce the by-product formation and improve the conversion rate of ethylene oxide.
  • CN105001058 discloses the use of Al modified Ti-MWW zeolite catalyst for the manufacturing MEG from Ee in one step using water as solvent and hydrogen peroxide as oxidizing agent.
  • CN101003376 discloses the use of a Ti-MWW zeolite catalyst chemically treated with an organic amine like piperidine or hexamethyleneimine, in chemical reactions among which the manufacture of epoxides and hydrogen peroxide as oxidizing agent. However, this document is silent about the manufacture of MEG.
  • This modified catalyst is very active in the synthesis of MEG from Ee with water as solvent and hydrogen peroxide as oxidizing agent.
  • the present invention relates to a process for the manufacture of ethylene glycol starting from ethylene (Ee) , said process using a reaction mixture comprising Ee, a Ti-MWW zeolite catalyst chemically treated with an organic amine, hydrogen peroxide and water.
  • Preferred embodiments are those according to which:
  • the organic amine is an aqueous solution of piperidine or hexamethyleneimine
  • the catalyst concentration in the reaction mixture is in the range of from 0.5 to 5.0 wt. %;
  • the process is performed at a temperature from 20°C to 150°C;
  • the molar ratio of hydrogen peroxide to Ee is in the range of from 0.01 to 10;
  • the molar ratio of water to hydrogen peroxide is in the range of from 5 to 50;
  • the molar ratio of water to Ee is in the range of from 1 to 50.
  • the reaction mixture also comprises a hydrogen peroxide stabilizer like a mineral acid, preferably nitric acid, and/or HEDP (1-hydroxy ethylidene-1, 1-diphosphonic acid) .
  • a hydrogen peroxide stabilizer like a mineral acid, preferably nitric acid, and/or HEDP (1-hydroxy ethylidene-1, 1-diphosphonic acid) .
  • the catalyst is preferably used as a slurry catalyst or a fixed bed catalyst.
  • the zeolite is preferably mixed with a binder like silica or alumina or a mixture thereof and then shaped for instance by extrusion.
  • An oxidative hydration reaction (OHR) for producing ethylene glycol is carried out under vigorous stirring in an autoclave reactor equipped with a 45 mL Telfon-inner.
  • methanol 5 g
  • hydrogen peroxide 1.13 g, 30 wt. %aqueous, 10 mmol of H2O2
  • the TS-1 catalyst was prepared according to the procedure described in U.S. Pat. No. 4,410,501.
  • the reaction mixture is immediately immersed in a pre-heated oil bath to start the reaction.
  • the reaction mixture is stirred at 40°C for 2 h, and then immediately cooled down in an ice bath to stop the reaction.
  • Both the gas and the liquid phase samples are collected and analyzed by gas chromatography (GC) using isopropanol as an internal standard.
  • GC gas chromatography
  • the gases are vented into an acetonitrile solvent for GC analysis.
  • the catalyst is removed from the reaction mixture by centrifugation and the supernatant is analyzed by GC for organic products and standard titration with 0.05 M Ce (SO4) 2 for hydrogen peroxide.
  • the oxidative hydration reaction is run according to the same procedure as Comparative Example 1 except that water (5 g) is used as a solvent instead of methanol.
  • the oxidative hydration reaction is run according to the same procedure as Comparative Example 1 except that Ti-MWW (0.1 g) is used as a catalyst instead of TS-1.
  • Ti-MWW 0.1 g
  • the Ti-MWW catalyst was prepared according to a known literature procedure (Chemistry Letters, 2000: 774) .
  • the oxidative hydration reaction is run according to the same procedure as Comparative Example 3 except that water (5 g) is used as a solvent instead of methanol.
  • the oxidative hydration reaction is run according to the same procedure as Comparative Example 4 except that Ti-MWW is chemically treated in an aqueous solution of piperidine according to a known literature procedure (Journal of Physical Chemistry C, 2008, 112, 6132) .
  • the oxidative hydration reaction is run according to the same procedure as Comparative Example 4 except that Ti-MWW is chemically treated in an aqueous solution of hexamethyleneimine according to a known literature procedure (Journal of Physical Chemistry C, 2008, 112, 6132) .
  • the oxidative hydration reaction is run according to the same procedure as Comparative Example 4 except that the amount of Ti-MWW is 0.2 g.
  • the oxidative hydration reaction is run according to the same procedure as Comparative Example 4 except that the pressure of ethylene is 5.0 MPa.
  • the oxidative hydration reaction is run according to the same procedure as Comparative Example 4 except that the amount of water is 2 g.
  • the oxidative hydration reaction is run according to the same procedure as Comparative Example 4 except that the reaction temperature is at 60°C.
  • the oxidative hydration reaction is run according to the same procedure as Example 5 except that the reaction temperature is at 60°C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Disclosed is a process for the manufacture of ethylene glycol starting ethylene using a reaction mixture comprising ethylene, a Ti-MWW zeolite catalyst chemically treated with an organic amine, hydrogen peroxide and water.

Description

    [Title established by the ISA under Rule 37.2] PROCESS FOR MANUFACTURE OF ETHYLENE GLYCOL
  • The present invention relates to a process for the manufacture of ethylene glycol starting from ethylene (Ee) .
  • Ethylene Glycol (Mono-Ethylene Glycol or MEG) is an important organic chemical raw material mainly used in the production of polyester (more precisely of PET or poly-ethylene-terephthalate) and as antifreeze agent.
  • At present, large-scale ethylene glycol production is generally made using a non-catalytic direct hydration method wherein ethylene oxide (EO) and water are reacted generally in a molar ratio of about 1: 20-22 (molar ratio) resulting in an ethylene glycol aqueous solution containing only about 10％ (mass fraction) of MEG, the rest being water and by-products like diethylene glycol (DEG) and triethylene glycol (TEG) . Increasing the amount of water used for this method can reduce the by-product formation and improve the conversion rate of ethylene oxide. However, it makes it necessary to set up multiple evaporators/distillation columns, increasing the equipment investment and energy consumption, which directly affects the production cost of ethylene glycol.
  • CN105001058 discloses the use of Al modified Ti-MWW zeolite catalyst for the manufacturing MEG from Ee in one step using water as solvent and hydrogen peroxide as oxidizing agent.
  • CN101003376 discloses the use of a Ti-MWW zeolite catalyst chemically treated with an organic amine like piperidine or hexamethyleneimine, in chemical reactions among which the manufacture of epoxides and hydrogen peroxide as oxidizing agent. However, this document is silent about the manufacture of MEG.
  • The inventors have now discovered that this modified catalyst is very active in the synthesis of MEG from Ee with water as solvent and hydrogen peroxide as oxidizing agent.
  • Therefore, the present invention relates to a process for the manufacture of ethylene glycol starting from ethylene (Ee) , said process using a reaction mixture comprising Ee, a Ti-MWW zeolite catalyst chemically treated with an organic amine, hydrogen peroxide and water.
  • Preferred embodiments are those according to which:
  • -the organic amine is an aqueous solution of piperidine or hexamethyleneimine；
  • -the catalyst concentration in the reaction mixture is in the range of from 0.5 to 5.0 wt. ％；
  • -the process is performed at a temperature from 20℃ to 150℃；
  • -the molar ratio of hydrogen peroxide to Ee is in the range of from 0.01 to 10；
  • -the molar ratio of water to hydrogen peroxide is in the range of from 5 to 50；
  • -the molar ratio of water to Ee is in the range of from 1 to 50.
  • Considering the fact that Ee-oxygen mixtures can be explosive, care should be taken to work in conditions outside the explosion zone.
  • In a preferred sub-embodiment, the reaction mixture also comprises a hydrogen peroxide stabilizer like a mineral acid, preferably nitric acid, and/or HEDP (1-hydroxy ethylidene-1, 1-diphosphonic acid) .
  • In the invention, the catalyst is preferably used as a slurry catalyst or a fixed bed catalyst. Hence, the zeolite is preferably mixed with a binder like silica or alumina or a mixture thereof and then shaped for instance by extrusion.
  • The following Examples illustrate some embodiments of the present invention.
  • COMPARATIVE EXAMPLE 1
  • An oxidative hydration reaction (OHR) for producing ethylene glycol is carried out under vigorous stirring in an autoclave reactor equipped with a 45 mL Telfon-inner. TS-1 (0.1 g, Si/Ti＝50) , methanol (5 g) and hydrogen peroxide (1.13 g, 30 wt. ％aqueous, 10 mmol of H2O2) are added into the reactor, then ethylene is charged into autoclave to replace the air inside three times and kept the reaction pressure at a constant of 2.5 MPa. The TS-1 catalyst was prepared according to the procedure described in U.S. Pat. No. 4,410,501. The reaction mixture is immediately immersed in a pre-heated oil bath to start the reaction. The reaction mixture is stirred at 40℃ for 2 h, and then immediately cooled down in an ice bath to stop the reaction.
  • Both the gas and the liquid phase samples are collected and analyzed by gas chromatography (GC) using isopropanol as an internal standard. The gases are vented into an acetonitrile solvent for GC analysis. The catalyst is removed from the reaction mixture by centrifugation and the supernatant is analyzed by GC for  organic products and standard titration with 0.05 M Ce (SO4) 2 for hydrogen peroxide.
  • COMPARATIVE EXAMPLE 2
  • The oxidative hydration reaction is run according to the same procedure as Comparative Example 1 except that water (5 g) is used as a solvent instead of methanol.
  • COMPARATIVE EXAMPLE 3
  • The oxidative hydration reaction is run according to the same procedure as Comparative Example 1 except that Ti-MWW (0.1 g) is used as a catalyst instead of TS-1. The Ti-MWW catalyst was prepared according to a known literature procedure (Chemistry Letters, 2000: 774) .
  • COMPARATIVE EXAMPLE 4
  • The oxidative hydration reaction is run according to the same procedure as Comparative Example 3 except that water (5 g) is used as a solvent instead of methanol.
  • EXAMPLE 5
  • The oxidative hydration reaction is run according to the same procedure as Comparative Example 4 except that Ti-MWW is chemically treated in an aqueous solution of piperidine according to a known literature procedure (Journal of Physical Chemistry C, 2008, 112, 6132) .
  • EXAMPLE 6
  • The oxidative hydration reaction is run according to the same procedure as Comparative Example 4 except that Ti-MWW is chemically treated in an aqueous solution of hexamethyleneimine according to a known literature procedure (Journal of Physical Chemistry C, 2008, 112, 6132) .
  • COMPARATIVE EXAMPLE 7
  • The oxidative hydration reaction is run according to the same procedure as Comparative Example 4 except that the amount of Ti-MWW is 0.2 g.
  • COMPARATIVE EXAMPLE 8
  • The oxidative hydration reaction is run according to the same procedure as Comparative Example 4 except that the pressure of ethylene is 5.0 MPa.
  • COMPARATIVE EXAMPLE 9
  • The oxidative hydration reaction is run according to the same procedure as Comparative Example 4 except that the amount of water is 2 g.
  • COMPARATIVE EXAMPLE 10
  • The oxidative hydration reaction is run according to the same procedure as Comparative Example 4 except that the reaction temperature is at 60℃.
  • EXAMPLE 11
  • The oxidative hydration reaction is run according to the same procedure as Example 5 except that the reaction temperature is at 60℃.
  • The results obtained in all these Examples are shown in Table 1 below.

Claims (9)

  1. A process for the manufacture of ethylene glycol starting ethylene (Ee) , said process using a reaction mixture comprising Ee, a Ti-MWW zeolite catalyst chemically treated with an organic amine, hydrogen peroxide and water.
  2. The process according to claim 1, wherein the organic amine is piperidine or hexamethyleneimine.
  3. The process according to any of the preceding claims, wherein the catalyst concentration in the reaction mixture is in the range of from 0.5 to 5.0 wt. ％.
  4. The process according to any of the preceding claims, wherein the process is performed at a temperature from 20℃ to 150℃.
  5. The process according to any of the preceding claims, wherein the molar ratio of hydrogen peroxide to Ee is in the range of from 0.01 to 10.
  6. The process according to the preceding claim, wherein the molar ratio of water to Ee is in the range of from 1 to 50.
  7. The process according to any of the preceding claims, wherein the reaction mixture also comprises a hydrogen peroxide stabilizer like a mineral acid, preferably nitric acid, and/or HEDP (1-hydroxy ethylidene-1, 1-diphosphonic acid) .
  8. The process according to any of the preceding claims, wherein the catalyst is a slurry catalyst or a fixed bed catalyst.
  9. The process according to the preceding claim, wherein the zeolite is mixed with a binder like silica, alumina or a mixture thereof and shaped by extrusion.
EP17916378.7A 2017-06-28 2017-06-28 PROCESS FOR PRODUCING ETHYLENE GLYCOL Withdrawn EP3645490A4 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2017/090518 WO2019000266A1 (en) 2017-06-28 2017-06-28 Process for manufacture of ethylene glycol

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EP3645490A1 true EP3645490A1 (en) 2020-05-06
EP3645490A4 EP3645490A4 (en) 2020-12-09

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119977757A (en) * 2023-11-13 2025-05-13 中国石油天然气股份有限公司 A method for continuously producing ethylene glycol from ethylene

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114797965B (en) * 2022-04-29 2023-05-23 浙江师范大学 A kind of titanium silicon molecular sieve catalyst for preparing ethylene glycol and preparation method thereof
CN116984024B (en) * 2023-06-21 2025-06-27 浙江师范大学 Preparation method of nitrogen-doped tungsten carbide/titanium silicon molecular sieve catalyst

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3800488B2 (en) * 2000-05-08 2006-07-26 株式会社日本触媒 Method for producing ethylene glycol
CN100460324C (en) * 2006-09-30 2009-02-11 华东师范大学 A kind of synthetic method of alkali-modified titanium-containing molecular sieve
CN102951998B (en) * 2011-08-24 2015-07-01 岳阳蓬诚科技发展有限公司 Method of preparing glycol by using one-step ethylene method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119977757A (en) * 2023-11-13 2025-05-13 中国石油天然气股份有限公司 A method for continuously producing ethylene glycol from ethylene

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Publication number Publication date
WO2019000266A1 (en) 2019-01-03
EP3645490A4 (en) 2020-12-09

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