WO2016099046A1 - Procédé de production de butadiène - Google Patents

Procédé de production de butadiène Download PDF

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Publication number
WO2016099046A1
WO2016099046A1 PCT/KR2015/012694 KR2015012694W WO2016099046A1 WO 2016099046 A1 WO2016099046 A1 WO 2016099046A1 KR 2015012694 W KR2015012694 W KR 2015012694W WO 2016099046 A1 WO2016099046 A1 WO 2016099046A1
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WO
WIPO (PCT)
Prior art keywords
butene
butadiene
reactor
oxygen
reaction
Prior art date
Application number
PCT/KR2015/012694
Other languages
English (en)
Korean (ko)
Inventor
최대흥
고동현
서명지
차경용
황예슬
강전한
남현석
이주혁
한상진
한준규
Original Assignee
(주) 엘지화학
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
Priority claimed from KR1020150164750A external-priority patent/KR101709412B1/ko
Application filed by (주) 엘지화학 filed Critical (주) 엘지화학
Priority to CN201580003031.5A priority Critical patent/CN105916579B/zh
Priority to US15/035,430 priority patent/US9751819B2/en
Priority to EP15853645.8A priority patent/EP3059219B1/fr
Priority to JP2016528895A priority patent/JP6321799B2/ja
Publication of WO2016099046A1 publication Critical patent/WO2016099046A1/fr

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/12—Alkadienes
    • C07C11/16—Alkadienes with four carbon atoms
    • C07C11/167—1, 3-Butadiene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/20—Use of additives, e.g. for stabilisation

Definitions

  • the present invention relates to a method for producing butadiene, and more particularly, to a method for producing butadiene in which the strength of the catalyst is maintained even in the oxidative dehydrogenation reaction to ensure long-term operation stability, and the selectivity is not reduced due to less side reactions.
  • 1,3-Butadiene is an intermediate of petrochemical products, and its demand and value are gradually increasing all over the world.
  • Methods for producing 1,3-butadiene include naphtha cracking, direct dehydrogenation of butenes, and oxidative dehydrogenation of butenes.
  • the oxidative dehydrogenation of butene is a reaction in which butene and oxygen react to generate 1,3-butadiene and water, which is very thermodynamically advantageous because stable water is produced.
  • the oxidative dehydrogenation of the butenes has a problem of increasing the reactor differential pressure due to the decrease in strength of the catalyst after the reaction.
  • an object of the present invention is to provide a butadiene production method in which the strength of the catalyst is maintained even in the oxidative dehydrogenation reaction to ensure long-term operating stability, and the side reaction is small so that the selectivity does not decrease. It is done.
  • the present invention is a method for producing butadiene by oxidative dehydrogenation by adding butene and oxygen in a reactor containing a metal composite oxide catalyst, the molar ratio of butene and oxygen is 1.8 to 2.2 It provides a butadiene production method characterized in that.
  • Butadiene production method of the present invention is a method for producing butadiene by injecting butene and oxygen in a reactor containing a metal composite oxide catalyst and oxidative dehydrogenation, characterized in that the molar ratio of butene and oxygen is 1.8 to 2.2. .
  • the molar ratio of butene and oxygen is less than 1.8, lattice oxygen in the catalyst is consumed and structural stability is deteriorated, and thus catalyst strength is lowered.
  • the molar ratio of butene and oxygen exceeds 2.2, by-products There is a problem that a lot of generated butadiene selectivity is lowered.
  • the butene may be, for example, 1-butene.
  • the butenes may be, for example, at least 95% pure, at least 98% pure, or at least 99% pure.
  • the oxidizing dehydrogenation is butene reference gas space velocity, for example (GHSV; Gas Hourly Space Velocity) is from 30 to 80 h - 1 BE (Butene) , 40 to 200 h - 1 BE, or 50 to 150 h - 1 BE days It is possible to achieve high conversion and selectivity within this range.
  • GHSV Gas Hourly Space Velocity
  • the reaction may further include one or more selected from the group consisting of, for example, steam, carbon dioxide and nitrogen.
  • butene: oxygen: steam: nitrogen is, for example, 1: 1.8 to 2.2: 1 to 12:10 to 30 and 1: 1.8 to 2.2: It may be 1 to 10:10 to 25 or 1: 1.8 to 2.2: 1 to 8:12 to 25, and within this range, there is an excellent operation stability and selectivity.
  • the oxidative dehydrogenation reaction may be carried out, for example, at a reaction temperature of 250 to 450 ° C, 290 to 400 ° C, or 290 to 350 ° C.
  • the reaction may further include, for example, recycling carbon dioxide discharged after the reaction when carbon dioxide is additionally added to the reactant.
  • the metal composite oxide catalyst may be, for example, a compound represented by Chemical Formula 1, in which case, butene conversion and butadiene selectivity may be excellent.
  • E is at least one selected from the group consisting of nickel, sodium, potassium, rubidium and cesium;
  • A, b, c, d, and e are 0.1 to 10, 0.1 to 10, 1 to 20, and 0 to 5 when a is 12;
  • Y is a value determined for fitting valences by other components.
  • the E may be, for example, cesium, potassium or a mixture thereof, in which case the butene conversion and butadiene selectivity are excellent.
  • the molar ratio of molybdenum: bismuth: iron: cobalt: cesium: potassium in Chemical Formula 1 is 12: 0.1-10: 0.1-10: 1-20: 0-5: 0-3 days And, as another example 12: 0.5 ⁇ 2: 0.5 ⁇ 2: 5 ⁇ 15: 0 ⁇ 1: 0 ⁇ 0.5, preferably 12: 0.8 ⁇ 2: 0.8 ⁇ 2: 6 ⁇ 10: 0 ⁇ It may be 0.9: 0 to 0.5, or 12: 0.8 to 2: 0.8 to 2: 6 to 10: 0.01 to 0.9: 0.01 to 0.5, and the conversion, selectivity, and yield of the product are excellent within this range.
  • the strength of the metal composite oxide catalyst is, for example, 3.0 or more kgf / cm 2 , 3.0 to 6.0 kgf / cm 2 , or 3.0 to 5.0 kgf / cm 2 , and the effect of excellent long-term operating safety and butadiene selectivity within this range is excellent. have.
  • the bismuth molybdate-based composite oxide catalyst may be prepared by the following steps, for example:
  • Each of the metal precursors used in step 1) is not particularly limited and may be conventionally used in the art.
  • the precursors of nickel, sodium, potassium, rubidium and cesium are not particularly limited, but ammonium chloride, carbonate, nitrate, acetate chloride of each metal, Oxide, etc.
  • the bismuth precursor may be bismuth nitrate, and the precursor of molybdenum may be ammonium molybdate.
  • Step 1) is a step of preparing a first solution by mixing each metal precursor material in a solvent in order to mix the metal components constituting the bismuth molybdate-based composite oxide.
  • the solvent may be distilled water, but is not particularly limited.
  • a strong acid is additionally added to the solvent, or the bismuth precursor is separated and dissolved in a solvent containing a strong acid, and then added to the mixed solution of the other metal precursor to prepare a first solution. can do.
  • the strong acid may be nitric acid, but is not limited thereto.
  • step 2) in order to mix the molybdenum precursor in the first solution, a molybdenum precursor is dissolved in a solvent to prepare a second solution, and then the first solution is added to mix and react.
  • the reaction may be performed while stirring, the stirring may be performed at a stirring speed of 100 to 800 rpm in the temperature range of 25 to 80 °C.
  • Step 3) is a step of obtaining a bismuth molybdate-based composite oxide by drying, molding and calcining the reactant produced after the reaction.
  • the firing may be performed for 1 to 24 hours at a temperature of 400 to 600 °C, for example, preferably may be performed for 2 to 10 hours at a temperature of 450 to 500 °C.
  • the reactor used for the oxidative dehydrogenation reaction is not particularly limited as long as it is typically a reactor that can be used in the art, and may be, for example, a tubular reactor, a tank reactor, a fluidized bed reactor, or a fixed bed reactor.
  • the stationary phase reactor may be, for example, a multi-tube reactor or a plate reactor.
  • the reactor may be, for example, a reactor which is installed in an electric furnace to maintain a constant reaction temperature of the catalyst layer, and the oxidative dehydrogenation reaction proceeds while the reactant continuously passes through the catalyst layer.
  • Bismuth nitrate pentahydrate (Bi (NO 3 ) 3 .5 (H 2 O)), iron nitrate hexahydrate (Fe (NO 3 ) 3 .9 (H 2 O)), cobalt nitrate hexahydrate (Co ( NO 3 ) 2 .6 (H 2 O)), potassium nitrate (KNO 3 ), and cesium nitrate (CsNO 3 ) were dissolved in distilled water to prepare a first solution. At this time, bismuth nitrate pentahydrate was dissolved separately in aqueous nitric acid solution and then added.
  • a second solution was prepared by dissolving ammonium molybdate tetrahydrate ((NH 4 ) 6 (Mo 7 O 24 ) .4 (H 2 O)) in distilled water.
  • the first solution was added to the second solution, followed by stirring at 40 ° C. for 1 hour to form a precipitate.
  • the precipitate was dried in an oven at 120 ° C. for 24 hours, and then calcined at 450 ° C. for 5 hours to form Mo 12.
  • ⁇ .8 2 Fe 0 .8 0 Bi 2 ⁇ 6 ⁇ Co 10 Cs 0.9 K 0.01 0 .01 ⁇ 0.5 ⁇ Oy (where y is a mole of oxygen atoms that satisfies the valence of the constituent elements other than oxygen)
  • a component bismuth molybdate catalyst was prepared.
  • 1-butene and oxygen were used as reactants, and additionally nitrogen and steam were introduced together.
  • a metal tubular reactor was used, and the metal composite oxide catalyst prepared above was charged so that the volume of the catalyst layer in contact with the reactant was fixed at 50 cc, and the steam was injected into the vaporizer in the form of water, and then at 340 ° C.
  • the reactor was designed to vaporize with steam and mix with other reactants 1-butene and oxygen to enter the reactor.
  • the amount of butene was controlled using a mass flow controller for liquids, oxygen and nitrogen were controlled using a mass flow controller for gases, and the amount of steam was controlled using a liquid pump.
  • the proportion of reactants and gas hourly space velocity (GHSV) were set based on 1-butene.
  • Example 1 The metal composite oxide catalyst used in Example 1 and Comparative Examples 1 to 6 and its reaction characteristics were measured by the following method, and the results are shown in Table 1 below.
  • Catalyst strength (kgf) The strength was measured in the horizontal direction by the tensile strength measuring device.
  • Oxygen reduction rate (%) in the catalyst It was measured using Energy-dispersive X-ray spectroscopy (EDX).
  • Example 1 the butadiene production method according to the present invention (Example 1) was hardly observed a decrease in the oxygen content and the catalyst strength in the catalyst, on the contrary, OBR as in the prior art, but Comparative Examples 1 to 3 When less than 1.8, it was confirmed that oxygen in the catalyst lattice was released during the reaction, thereby decreasing the strength of the catalyst.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un procédé de production de butadiène et, plus spécifiquement, un procédé de production de butadiène consistant à introduire du butène et de l'oxygène dans un réacteur contenant un catalyseur d'oxyde composite métallique et à soumettre celui-ci à une déshydrogénation oxydative, le procédé de production de butadiène étant caractérisé en ce que le rapport molaire de butène à l'oxygène est de 1,8 à 2,2. La présente invention a pour but de réaliser un procédé de production de butadiène qui assure une stabilité de fonctionnement à long terme en maintenant la résistance d'un catalyseur, même si celui-ci est soumis à la déshydrogénation oxydative et ne fait pas diminuer la sélectivité par réduction d'une réaction secondaire.
PCT/KR2015/012694 2014-12-16 2015-11-25 Procédé de production de butadiène WO2016099046A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201580003031.5A CN105916579B (zh) 2014-12-16 2015-11-25 制备丁二烯的方法
US15/035,430 US9751819B2 (en) 2014-12-16 2015-11-25 Method of preparing butadiene
EP15853645.8A EP3059219B1 (fr) 2014-12-16 2015-11-25 Procédé de production de butadiène
JP2016528895A JP6321799B2 (ja) 2014-12-16 2015-11-25 ブタジエンの製造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20140181338 2014-12-16
KR10-2014-0181338 2014-12-16
KR1020150164750A KR101709412B1 (ko) 2014-12-16 2015-11-24 부타디엔 제조방법
KR10-2015-0164750 2015-11-24

Publications (1)

Publication Number Publication Date
WO2016099046A1 true WO2016099046A1 (fr) 2016-06-23

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WO (1) WO2016099046A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110004041A1 (en) * 2008-03-28 2011-01-06 Sk Energy Co., Ltd. Method of producing 1,3-butadiene from n-butene using continuous-flow dual-bed reactor
JP2011006395A (ja) 2009-05-29 2011-01-13 Mitsubishi Chemicals Corp 共役ジエンの製造方法
KR20110106181A (ko) * 2010-03-22 2011-09-28 금호석유화학 주식회사 비스무스-몰리브덴-철-인 다성분계 금속산화물 촉매와 그의 제조방법 및 이를 이용한 1,3-부타디엔의 제조방법
KR20110130130A (ko) * 2010-05-27 2011-12-05 금호석유화학 주식회사 ＢｉＰＯ４를 포함하는 다성분계 금속산화물 촉매와 그의 제조방법 및 이를 이용한 1,3-부타디엔의 제조방법
US20130281748A1 (en) * 2011-06-30 2013-10-24 Lg Chem, Ltd. Method for preparing 1,3-butadiene as high yield
KR20140131870A (ko) * 2013-05-06 2014-11-14 주식회사 엘지화학 부타디엔 제조를 위한 산화촉매 및 그 제조방법

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110004041A1 (en) * 2008-03-28 2011-01-06 Sk Energy Co., Ltd. Method of producing 1,3-butadiene from n-butene using continuous-flow dual-bed reactor
JP2011006395A (ja) 2009-05-29 2011-01-13 Mitsubishi Chemicals Corp 共役ジエンの製造方法
US20120130137A1 (en) * 2009-05-29 2012-05-24 Mitsubishi Chemical Corporation Production process of conjugated diene
KR20110106181A (ko) * 2010-03-22 2011-09-28 금호석유화학 주식회사 비스무스-몰리브덴-철-인 다성분계 금속산화물 촉매와 그의 제조방법 및 이를 이용한 1,3-부타디엔의 제조방법
KR20110130130A (ko) * 2010-05-27 2011-12-05 금호석유화학 주식회사 ＢｉＰＯ４를 포함하는 다성분계 금속산화물 촉매와 그의 제조방법 및 이를 이용한 1,3-부타디엔의 제조방법
US20130281748A1 (en) * 2011-06-30 2013-10-24 Lg Chem, Ltd. Method for preparing 1,3-butadiene as high yield
KR20140131870A (ko) * 2013-05-06 2014-11-14 주식회사 엘지화학 부타디엔 제조를 위한 산화촉매 및 그 제조방법

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