WO2020262774A1 - Procédé de production de polybutène, appareil de production de polybutène et polybutène ainsi produit - Google Patents

Procédé de production de polybutène, appareil de production de polybutène et polybutène ainsi produit Download PDF

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Publication number
WO2020262774A1
WO2020262774A1 PCT/KR2019/015671 KR2019015671W WO2020262774A1 WO 2020262774 A1 WO2020262774 A1 WO 2020262774A1 KR 2019015671 W KR2019015671 W KR 2019015671W WO 2020262774 A1 WO2020262774 A1 WO 2020262774A1
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WO
WIPO (PCT)
Prior art keywords
polybutene
reactor
catalyst
tubular reactor
hydrogenation
Prior art date
Application number
PCT/KR2019/015671
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English (en)
Korean (ko)
Inventor
최준걸
조혜란
이도훈
유연식
신학수
Original Assignee
한화토탈 주식회사
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Application filed by 한화토탈 주식회사 filed Critical 한화토탈 주식회사
Publication of WO2020262774A1 publication Critical patent/WO2020262774A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/08—Butenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • C08F4/12—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of boron, aluminium, gallium, indium, thallium or rare earths
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/70—Iron group metals, platinum group metals or compounds thereof
    • C08F4/7095—Cobalt, nickel or compounds thereof
    • C08F4/7098—Nickel or compounds thereof

Definitions

  • the present invention relates to a method for producing high-performance polybutene from which a halogen component is removed, a production apparatus, and a polybutene produced thereby.
  • Polybutene is a polymerization of an olefin component having 4 carbon atoms, which is generally derived from the decomposition process of naphtha, and uses high purity isobutene, C4 raffinate-1, and butane-butene fraction (BB fraction). It is manufactured using as.
  • organic halogen Due to the high content of organic halogen, it is difficult to directly use it as a fuel additive using a low molecular weight polymer, a friction reducing agent, a non-romantic organic solvent, and a cosmetic additive, and a low molecular weight polymer containing a halogen component (Light Polymer) Are sold only as waste or low-cost fuel oil.
  • U.S. Patent No. 7,365,152 discloses a method of removing fluorine contained in highly reactive polybutene prepared using a Lewis acid-based catalyst. Disclosed is a method of preparing a highly reactive polybutene with a low fluorine content by diluting the highly reactive polybutene prepared by the above method in a solvent and passing through an alumina column impregnated with a compound for removing fluorine, but an additional process after polybutene production As a result, there is a disadvantage that the installation of an adsorption column and periodic replacement of the adsorbent are required, and a process of removing the solvent from the removed polybutene solution has to be added.Therefore, a method capable of producing polybutene with reduced halogen content more economically and The demand for the device continues.
  • the present invention provides a method for producing a high-performance polybutene from which a halogen component has been removed, a production apparatus, and a polybutene produced thereby.
  • the present invention comprises the steps of: (a) polymerizing polybutene by supplying a reaction raw material to a polybutene reactor;
  • step (c) removing a halogen component from the polybutene of step (b) in a fixed tubular reactor including a hydrogen supply device and a catalyst for hydrogenation;
  • the fixed tubular reactor in step (c) has a weight hourly space velocity (WHSV) of 50 to 200, and a hydrogen pressure of 1 to 10 kgf/cm 2 .
  • WHSV weight hourly space velocity
  • the present invention is a polybutene production apparatus in which a fixed-bed reactor including a low molecular weight removal device, a hydrogen supply device, and a catalyst for hydrogenation are sequentially connected to the rear end of the polybutene reactor,
  • a scrubber for treating acidic gas is connected to the fixed tubular reactor,
  • the fixed tubular reactor has a weight hourly space velocity (WHSV) of 50 to 200, and a hydrogen pressure of 1 to 10 kgf/cm 2 .
  • WHSV weight hourly space velocity
  • the present invention provides a polybutene manufactured by the above manufacturing method or manufactured by the above manufacturing apparatus.
  • the method and apparatus for producing polybutene of the present invention provides high-performance polybutene from which halogen components are removed.
  • the method and apparatus for producing polybutene according to the present invention can increase production efficiency by providing polybutene having a halogen component content of close to 0 ppm and a high olefin content without a separate additional process.
  • the present invention comprises the steps of: (a) polymerizing polybutene by supplying a reaction raw material to a polybutene reactor;
  • step (c) removing a halogen component from the polybutene of step (b) in a fixed tubular reactor including a hydrogen supply device and a catalyst for hydrogenation;
  • the fixed tubular reactor in step (c) has a weight hourly space velocity (WHSV) of 50 to 200, and a hydrogen pressure of 1 to 10 kgf/cm 2 .
  • WHSV weight hourly space velocity
  • the low molecular weight polybutene refers to polybutene of C 20 or less.
  • the present invention is a polybutene production apparatus in which a fixed-bed reactor including a low molecular weight removal device, a hydrogen supply device, and a catalyst for hydrogenation are sequentially connected to the rear end of the polybutene reactor,
  • a scrubber for treating acidic gas is connected to the fixed tubular reactor,
  • the fixed tubular reactor has a weight hourly space velocity (WHSV) of 50 to 200, and a hydrogen pressure of 1 to 10 kgf/cm 2 .
  • WHSV weight hourly space velocity
  • a raw material supply line is directly connected to the polybutene reactor to supply the reaction raw material.
  • the kind of the reaction raw material is not particularly limited as long as it is an olefin compound having 4 carbon atoms, but may be, for example, a fraction of 4 carbon atoms, a 4 carbon number LPG (liquefied petroleum gases), and mixtures thereof.
  • the polybutene reactor may be a polymerization of polybutene by adding a polybutene polymerization catalyst together with the above-described reaction raw material.
  • the catalyst may be used without particular limitation as long as it is a conventional catalyst used for polybutene polymerization.
  • the catalyst may include at least one selected from an aluminum chloride catalyst and a boron trifluoride complex catalyst.
  • the type of the polybutene reactor is not particularly limited, and may be one selected from a continuous stirring tank reactor (CSTR), a batch reactor, and a tubular reactor.
  • the polybutene reactor may be a continuous stirring tank reactor (CSTR), and two or more continuous stirring tank reactors (CSTR) may be connected in parallel.
  • the polymerization of polybutene in the polybutene reactor may be carried out under normal reaction conditions, and in consideration of molecular weight, the reaction is preferably carried out at a temperature of -25 to 50 °C, and 7 kgf so that the raw material can maintain a liquid state. It may be economical to set the pressure at a pressure of /cm 2 or more, and to react for a residence time of 90% or more and a reaction time of 5 to 60 minutes, preferably 10 to 30 minutes. After the reaction of the polybutene, neutralization, washing, and solvent recovery may be additionally performed.
  • the prepared polybutene may remove low molecular weight polybutene (LMPIB) by passing through a low molecular weight removal device.
  • LMPIB low molecular weight polybutene
  • a vacuum purification tower may be used as the low molecular weight removal device.
  • the process conditions of the low molecular weight removal device are not particularly limited, and for example, may be performed under conditions of 180 to 230° C. and 5 to 50 mbar.
  • LMPIB low molecular weight polybutene
  • the polybutene includes the step of passing through a fixed tubular reactor including a hydrogen supply device and a catalyst for hydrogenation.
  • the polybutene may remove the halogen component contained in the polybutene by passing through a fixed tubular reactor including a hydrogen supply device and a catalyst for hydrogenation.
  • the process conditions of the hydrogen supply device are not particularly limited, and for example, may be performed under conditions of 120 to 200° C. and 2 to 5 kgf/cm 2 .
  • the type of the catalyst for the hydrogenation reaction is not particularly limited, but, for example, a Group 10 metal compound such as Ni, Pd, and Pt may be used.
  • the polybutene includes the step of removing an acidic gas component through a scrubber.
  • the scrubber can remove acid gases generated as by-products in the process step, and can efficiently treat various waste gases containing acidic gas components such as hydrogen chloride, hydrogen fluoride, sulfur oxide, nitrogen oxide, hydrogen sulfide, and sulfurous acid gas.
  • the scrubber may be connected to the fixed tubular reactor.
  • the scrubber may employ a commonly known structure, and for example, a compressed air supply conduit, a scrubber storage tank, a waste gas supply conduit, a return pipe, and the like may be used.
  • the present invention provides polybutene, characterized in that it is manufactured by the above manufacturing method and manufacturing apparatus.
  • Polybutene produced by the above manufacturing method and manufacturing apparatus has a halogen content close to 0 ppm, so it can be used as a fuel additive, a friction reducing agent, an organic solvent, and a cosmetic additive without any additional process after manufacturing, and has excellent olefin content. There is an advantage.
  • the polybutene manufactured by the above manufacturing method and manufacturing apparatus may be a non-reactive polybutene.
  • the non-reactive polybutene may have a vinylidene content of less than 20% by weight at a molecular end and a number average molecular weight of 200 to 5,000 g/mol, preferably 300 to 2,500 g/mol.
  • the polymerized polymer was transferred to a neutralization tank, neutralized and washed with an aqueous sodium hydroxide solution, and only the organic matter in the upper layer was recovered from a settler, and C4-LPG, a solvent, was recovered and the remaining polybutene was transferred to a reduced pressure polybutene purification tower. Moving and removing the C 20 or less low molecular weight polybutene (LMPIB) under the condition of 210 °C, 20 mbar to prepare a non-reactive polybutene.
  • LMPIB low molecular weight polybutene
  • the prepared polybutene at about 150°C supplies hydrogen to the rear end of the polybutene refining tower at a pressure of 3 kgf/cm 2 , and is placed in a fixed-bed reactor containing nickel-supported alumina, a catalyst for hydrogenation.
  • WHSV weight hourly space velocity
  • the pressure of the hydrogen supply device, the WHSV of the fixed tubular reactor, the chlorine content and olefin content of the prepared polybutene are shown in Table 1 below.
  • Polybutene according to Comparative Example 1-3 was prepared in the same manner as in Example 1-3, except that the weight hourly space velocity (WHSV) was adjusted not to exceed 10.
  • WHSV weight hourly space velocity
  • the pressure of the hydrogen supply device, the WHSV of the fixed tubular reactor, the chlorine content and olefin content of the prepared polybutene are shown in Table 1 below.
  • the polymerized polymer was transferred to a neutralization tank, neutralized and washed with an aqueous sodium hydroxide solution, and only the organic matter in the upper layer was recovered from a settler, and C4-LPG, a solvent, was recovered and the remaining polybutene was transferred to a reduced pressure polybutene purification tower. Moving and removing low-molecular polybutene (LMPIB) under conditions of 210° C. and 20 mbar to prepare non-reactive polybutene.
  • LMPIB low-molecular polybutene
  • the pressure of the hydrogen supply device, the chlorine content and the olefin content of the prepared polybutene are shown in Table 1 below.
  • Example 1 108 ⁇ 0.1 100
  • Example 2 3 80 ⁇ 0.1 98
  • Example 3 50 ⁇ 0.1 80 Comparative Example 1 3 3 ⁇ 0.1 50 Comparative Example 2 60 3 ⁇ 0.1 3.4 Comparative Example 3 30 3 ⁇ 0.1 7.7 Comparative Example 4 3 0 10 100

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un procédé de production de polybutène hautement fonctionnel avec un composant halogène retiré de celui-ci, un appareil de production pour celui-ci, et le polybutène ainsi produit.
PCT/KR2019/015671 2019-06-24 2019-11-15 Procédé de production de polybutène, appareil de production de polybutène et polybutène ainsi produit WO2020262774A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020190075159A KR102189509B1 (ko) 2019-06-24 2019-06-24 폴리부텐 제조방법, 폴리부텐 제조장치 및 이에 의해 제조된 폴리부텐
KR10-2019-0075159 2019-06-24

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101481188B1 (ko) * 2006-12-12 2015-01-09 셰브런 유.에스.에이.인크. 알킬레이트 또는 알킬레이트 가솔린에서 유기 할라이드의 농도를 감소시키는 알킬화 방법
KR20150005206A (ko) * 2013-07-05 2015-01-14 대림산업 주식회사 폴리부텐 제조 시 발생되는 폐수의 처리 장치 및 방법
KR20150025211A (ko) * 2013-08-28 2015-03-10 대림산업 주식회사 폴리부텐 제조 시 발생되는 할로겐의 제거 장치 및 방법
WO2016150600A1 (fr) * 2015-03-25 2016-09-29 Haldor Topsøe A/S Élimination des halogénures contenus dans des hydrocarbures liquides
KR20180068533A (ko) * 2016-12-14 2018-06-22 한화토탈 주식회사 폴리부텐의 제조방법, 이에 의해 제조된 폴리부텐, 및 이에 의해 제조된 폴리부텐의 제조장치

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101481188B1 (ko) * 2006-12-12 2015-01-09 셰브런 유.에스.에이.인크. 알킬레이트 또는 알킬레이트 가솔린에서 유기 할라이드의 농도를 감소시키는 알킬화 방법
KR20150005206A (ko) * 2013-07-05 2015-01-14 대림산업 주식회사 폴리부텐 제조 시 발생되는 폐수의 처리 장치 및 방법
KR20150025211A (ko) * 2013-08-28 2015-03-10 대림산업 주식회사 폴리부텐 제조 시 발생되는 할로겐의 제거 장치 및 방법
WO2016150600A1 (fr) * 2015-03-25 2016-09-29 Haldor Topsøe A/S Élimination des halogénures contenus dans des hydrocarbures liquides
KR20180068533A (ko) * 2016-12-14 2018-06-22 한화토탈 주식회사 폴리부텐의 제조방법, 이에 의해 제조된 폴리부텐, 및 이에 의해 제조된 폴리부텐의 제조장치

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