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WO2009006815A1 - Procédé de protection d'un catalyseur utilisé pour la préparation d'un ester gras inférieur - Google Patents

Procédé de protection d'un catalyseur utilisé pour la préparation d'un ester gras inférieur Download PDF

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Publication number
WO2009006815A1
WO2009006815A1 PCT/CN2008/071388 CN2008071388W WO2009006815A1 WO 2009006815 A1 WO2009006815 A1 WO 2009006815A1 CN 2008071388 W CN2008071388 W CN 2008071388W WO 2009006815 A1 WO2009006815 A1 WO 2009006815A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
reaction
olefin
fatty acid
acid
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.)
Ceased
Application number
PCT/CN2008/071388
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English (en)
Chinese (zh)
Inventor
Xiannian Hu
Hua Li
Pingxiang Xi
Yudong Liu
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.)
Hunan Zhongchuang Chemical Co Ltd
Original Assignee
Hunan Zhongchuang Chemical Co Ltd
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Application filed by Hunan Zhongchuang Chemical Co Ltd filed Critical Hunan Zhongchuang Chemical Co Ltd
Publication of WO2009006815A1 publication Critical patent/WO2009006815A1/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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08—Ion-exchange resins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds

Definitions

  • This invention relates to a process for the protection of catalysts, and more particularly to a process for protecting a catalyst for the preparation of lower fatty acid esters.
  • ion exchange resin as a catalyst to catalyze the reaction of lower fatty acids and lower olefins to synthesize lower fatty acid esters generally has a better reaction effect.
  • ion exchange resin catalysts have low chemical stability and thermal stability, and are prone to swelling or loss of active components in long-term use, which in turn leads to catalyst deactivation.
  • U.S. Patent 5,457,228 discloses the use of a styrene sulfonic acid ion exchange resin or a phenol sulfonic acid resin as a catalyst to catalyze the reaction of acetic acid with propylene to form isopropyl acetate or acetic acid with 1-butene or 2-butene to produce sec-butyl acetate.
  • the process is characterized in that the tubular fixed bed reactor and the reaction material mixing cycle are used to effectively control the reaction temperature, avoid catalyst corrosion, slow down the catalyst deactivation, and inhibit the reverse reaction rate and the olefin polymerization side reaction.
  • organic carboxylic acids and chain olefins as raw materials may contain a small amount of metal ions, basic substances and sulfur-containing substances, which can be adsorbed on the ion exchange resin, causing catalyst loss. live.
  • the olefin used is a mixed hydrocarbon, such as when C4 is mixed, the diene and isobutylene in the mixed C4 are liable to coke, thereby causing the catalyst to be deactivated.
  • the applicant's patent application No. 200710200147.5 discloses a method of pretreating a reaction raw material with an ion exchange resin-based protective agent before the reaction to thereby prolong the service life of the catalyst.
  • the method can effectively protect the reaction catalyst and prolong its catalytic activity.
  • the exchange capacity of the protective agent is limited, when the catalyst toxin is contained in the reaction raw material, the protective agent is also susceptible to the toxicity of the catalyst toxin and gradually loses the protective property.
  • the mixed C4 contains a small amount of metal ions, a basic substance, a sulfur-containing substance, and a sludge, and the metal ion, the alkaline substance, and the sulfur-containing substance are catalyst poisons, and the sludge is Attached to the surface of the catalyst, causing catalyst deactivation.
  • the technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and to provide a method for protecting a catalyst for preparing a lower fatty acid ester which can effectively prevent catalyst poisoning and keep the catalyst active for a long period of time.
  • Preparation of lower fatty acid esters by reacting C1 ⁇ C4 fatty acids with C2 ⁇ C5 olefins is an industrial acquisition in the prior art
  • a preferred process for the lower fatty acid ester, wherein the molar ratio of the reactant C1 to C4 fatty acid to the C2 to C5 olefin (referred to as the acid to olefin ratio) is 0.7 to 3.0, preferably 0.8 to 2.5, because the acid to ene ratio is low.
  • the space velocity (feed space velocity) relative to the catalyst bed is 0.1 to 10.0 hr - preferably O S.
  • Ohr - 1 if the feed space velocity is lower than 0.1 hr - 1 , the reaction efficiency is low, and the side reaction is increased.
  • the space velocity is higher than lO.Ohr- 1 , the reaction conversion rate will decrease; the reaction temperature is 30 to 150 ° C, preferably 65 to 135 ° C.
  • the reaction pressure is not particularly strict, but generally should be controlled at 0.8 to 2.0 MPa, preferably 0.8 to 1.8 MPa, the purpose is to At the reaction temperature, the reactant olefin can Preferably dissolved in a lower fatty acid.
  • the reaction is carried out in a tubular fixed bed reactor in which industrial pure titanium containing a catalyst is used (a reactor which is preferably made of industrial pure titanium because of the organic carboxylic acid contained in the reaction raw material, which is easy to corrode the reaction equipment).
  • the reaction is carried out in the liquid phase to prepare a lower fatty acid ester.
  • the C1 to C4 fatty acid is a fatty acid having 1 to 4 carbon atoms, and may be formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid or acrylic acid, with acetic acid being preferred.
  • the C2 ⁇ C5 olefin is selected from one or more of ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, preferably propylene, 1-butene And / or 2-butene.
  • a catalyst a catalyst installed in a tubular fixed bed reactor
  • a strongly acidic ion exchange resin having a specific surface area. 20 to 50 m 2 /g, a pore volume of 0.1 to 0.3 ml/g, and a particle size of 0.1 to 1.5 mm.
  • the hydrocarbon material as a reaction raw material may contain metal ions, a basic substance, and a sulfur-containing substance, and these metal ions, a basic substance, and a sulfur-containing substance may cause deactivation of the strongly acidic ion exchange resin catalyst.
  • the catalyst protection method of the present invention is a method for protecting the strongly acidic ion exchange resin catalyst, that is, pretreatment of the reaction raw material before entering the reactor to remove harmful impurities in the reaction raw material, thereby preventing catalyst poisoning. .
  • the technical solution proposed by the present invention is a method for protecting a catalyst for preparing a lower fatty acid ester, which is characterized in that: when a lower fatty acid ester is prepared by using a C1 ⁇ C4 fatty acid and a C2 ⁇ C5 olefin, before the reaction First, the C2 ⁇ C5 olefin is washed with water, dehydrated after washing with water, and then the C1 ⁇ C4 fatty acid and the dehydrated olefin, or only one of them is subjected to a pretreatment apparatus equipped with a reaction aid. After the treatment, the above-mentioned treated raw materials C1 to C4 fatty acids and C2 to C5 olefins are fed to a reactor to prepare a lower fatty acid ester.
  • the hydrocarbon material containing C2 ⁇ C5 olefin is introduced before the reaction raw material enters the reactor.
  • a part of the toxin and the sludge of the above catalyst contained in the olefin can be washed away by water washing, thereby protecting the catalyst.
  • the flow rate of the washing water should be controlled to a certain extent, and the mass flow ratio of the washing water to the hydrocarbon substance can be controlled to 0 to 10, preferably 0 to 3. In general, the mass flow ratio of the washing water to the hydrocarbon material is increased, and the water washing effect is good.
  • the washing water can also be placed in a washing tower, a washing tank or a washing tank. At this time, the mass flow rate of the washing water is 0, and the hydrocarbon substance is washed with water to achieve a water washing effect. Washed water is generally available with demineralized water.
  • the dehydration method adopted by those skilled in the art can be used as an optional dewatering measure of the technical solution, such as the hydrocarbon intermediate tank after water washing or water washing, and the hydrocarbon substance is agglomerated by dehydration.
  • the coalescing device of the filter element, and the like can be used as an optional dewatering measure of the technical solution, such as the hydrocarbon intermediate tank after water washing or water washing, and the hydrocarbon substance is agglomerated by dehydration.
  • Another pretreatment in the above technical solution is to remove the C1 ⁇ C4 fatty acid and the dehydrated hydrocarbon material, or only the C1 ⁇ C4 fatty acid through a pretreatment device equipped with a reaction aid to remove harmful impurities.
  • the reaction aid in the preprocessor is an ion exchange resin, and the exchange capacity is not particularly controlled, but it is generally not less than 3 mmol/gH.
  • Examples of alternative ion exchange resins are S54 ion exchange resin or D72 ion exchange resin.
  • the temperature of the pre-processor can be 20 ⁇ 80 °C, the purpose of which is to fully absorb harmful impurities in the material under the condition of ensuring smooth flow, so that the diene and isobutylene in the hydrocarbon substance (such as mixed C4) and The organic carboxylic acid is reacted.
  • reaction auxiliaries one is to remove the metal ions contained in the reaction raw materials; the other is to adsorb the nitrogen-containing substances and sulfur-containing substances in the reaction raw materials; the third is when the olefins used are mixed hydrocarbon substances ( For example, when C4 is mixed, the diene and isobutylene in the mixed hydrocarbon are first reacted with the organic carboxylic acid to avoid coking in the reactor.
  • the present invention has the advantages that: in the above reaction for preparing a lower fatty acid ester by reacting a C1 ⁇ C4 fatty acid with a C2 ⁇ C5 olefin, the harmful impurities contained in the reaction raw material before being introduced into the reactor have been removed. In addition, this prevents poisoning of the catalyst used in the subsequent preparation reaction.
  • the catalyst After the treatment by the method of the present invention, the catalyst has no deactivation phenomenon after being used for more than 6 months, and the reaction aid which acts as a catalyst protection has no metal ion permeation phenomenon, and the pressure difference before and after the reaction auxiliary bed layer changes. Not big.
  • the purity of acetic acid was 99.5%
  • the mass composition of mixed C4 was: 1-butene 4.72%, 2-butene 49.22% butane 46.01%, isobutylene 0.05%.
  • the desalted water and the mixed C4 were passed to the water wash tower at a mass flow ratio of 5.
  • the water-washed mixed C4 and acetic acid were passed to a pretreatment apparatus equipped with a D72 type ion exchange resin, and the outlet temperature of the preprocessor was 70 °C.
  • the pretreated acetic acid and the mixed C4 were continuously fed into the tubular fixed bed reactor of the industrial pure titanium containing the catalyst from the bottom of the reactor, and the molar ratio of the acetic acid to the butene in the mixed C4 (acid to olefin ratio) was 1.3.
  • the feed mode is liquid phase feed
  • the acetic acid feed space velocity is l.Ohf 1
  • the reaction pressure is 1.6 MPa
  • the reaction temperature is 110 °C.
  • the composition of the reaction product was sampled every 8 hr and analyzed by gas chromatography. Determination of sec-butyl acetate selectivity
  • the concentration of Fe, Cr and Ni ions in the reaction medium after the pretreatment is less than 0.01 ⁇ ⁇ / ⁇ , and the pressure difference between the reaction aid bed and the bed is less than 0.1 MPa.
  • the catalyst activity was stable, and the reaction conversion rate and selectivity did not change significantly.
  • the concentration of Fe, Cr and Ni ions in the reaction medium after pre-processor was less than 0.01 ⁇ ⁇ / ⁇ , the pressure difference between the reaction aid bed and the bed Less than 0.1 MPa.
  • a strongly acidic ion exchange resin having a specific surface area of 30 m 2 /g, a pore volume of 0.25 ml/g, and a particle size of 1.0 mm was used as a catalyst.
  • a total of 3.5 t of the catalyst was charged into the split tubular reactor, and both ends of the catalyst layer were packed with styrene-divinylbenzene polymerized beads.
  • the mixed C4 and acetic acid were passed to a pretreatment apparatus equipped with a D72 type ion exchange resin, and the outlet temperature of the preprocessor was 70 °C.
  • the pretreated acetic acid and the mixed C4 were continuously fed into the reactor from the bottom of the reactor, and the molar ratio of the acetic acid to the butene in the mixed C4 (acid to olefin ratio) was 1.3, and the feed mode was liquid phase feed, acetic acid feed airspeed. It is l.Ohr- 1 , the reaction pressure is 1.6 MPa, and the reaction temperature is 110 °C.
  • the composition of the reaction product was sampled every 8 hr and analyzed by gas chromatography. The selectivity of sec-butyl acetate was determined to be above 98%.
  • the concentration of Fe, Cr and Ni ions in the reaction medium after the pretreatment is less than 0.01 ⁇ ⁇ / ⁇
  • the pressure difference between the reaction aid bed and the bed is less than 0.1 MPa.
  • the pressure difference between the reaction aid bed and the bed began to increase slightly.
  • the Fe ion concentration in the reaction medium after the pre-processor reached 9.6 ⁇ ⁇ / ⁇
  • the pressure difference between the reaction aid bed and the bed reached 0.4 MPa.
  • the desalted water and the mixed C4 were passed to the water wash tower at a mass flow ratio of 5.
  • the acetic acid was passed to a pretreatment apparatus equipped with a D72 type ion exchange resin, and the outlet temperature of the preprocessor was 70 °C.
  • the reactor was continuously fed from the bottom of the reactor, and the molar ratio of the acetic acid to the butene in the mixed C4 (acid to olefin ratio) was 1.3, and the feed mode was a liquid phase feed.
  • the acetic acid feed space velocity was 1.0 Ohf 1
  • the reaction pressure was 1.6 MPa
  • the reaction temperature was 110 °C.
  • the composition of the reaction product was sampled every 8 hr and analyzed by gas chromatography.
  • the selectivity of sec-butyl acetate was determined to be above 98%.
  • the concentration of Fe, Cr and Ni ions in the reaction medium after the pretreatment is less than 0.01 ⁇ ⁇ / ⁇ , and the pressure difference between the reaction aid bed and the bed is less than 0.1 MPa.
  • the catalyst activity was stable, and the reaction conversion rate and selectivity did not change significantly.
  • the concentration of Fe, Cr and Ni ions in the reaction medium after the pre-processor was less than 0.01 ⁇ ⁇ / ⁇ , the pressure difference between the reaction aid bed and the bed Less than 0.1 MPa.
  • a strongly acidic ion exchange resin having a specific surface area of 30 m 2 /g, a pore volume of 0.25 ml/g, and a particle size of 1.0 mm was used as a catalyst.
  • a total of 3.5 t of catalyst was charged to the split tube reactor. Both ends of the catalyst layer are packed with styrene-divinylbenzene polymerized beads.
  • the acetic acid was passed to a pretreatment apparatus equipped with a D72 type ion exchange resin, and the outlet temperature of the preprocessor was 70 °C.
  • the reactor was continuously fed from the bottom of the reactor, and the molar ratio of the acetic acid to the butene in the mixed C4 (acid to olefin ratio) was 1.3, and the feed mode was a liquid phase feed.
  • the acetic acid feed space velocity was 1.0 Ohf 1
  • the reaction pressure was 1.6 MPa
  • the reaction temperature was 110 °C.
  • the composition of the reaction product was sampled every 8 hr and analyzed by gas chromatography.
  • the selectivity of sec-butyl acetate was determined to be above 98%. After 80 days of operation, the catalyst activity was stable, and the reaction conversion rate and selectivity did not change significantly.
  • the concentration of Fe, Cr and Ni in the reaction medium after the pretreatment was less than 0.01 ⁇ g/g, and the pressure difference before and after the reaction aid bed was less than 0.1 MPa.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention porte sur un procédé de protection d'un catalyseur utilisé pour la préparation d'un ester gras inférieur. Un catalyseur consistant en une résine échangeuse d'ions acides est protégé par lavage des oléfines à 2-5 carbones pour éliminer une partie du poison du catalyseur dans l'oléfine avant qu'elles n'entrent dans le réacteur; et élimination des substances nocives d'acide gras à 1-4C et/ou d'oléfine à 2-5C à l'aide d'un agent auxiliaire de réaction dans un pré-réacteur. L'avantage de l'invention est que le procédé empêche l'empoisonnement du catalyseur étant donné que les impuretés nocives ont été éliminées, de telle sorte que le catalyseur ne perdra pas son aptitude à la réaction lorsqu'il sera utilisé plus de 6 mois, en même temps l'agent auxiliaire de réaction pour protéger le catalyseur n'a pas de phénomène de filtration croisée des ions métalliques, et il y a une petite différence de pression entre les couches de lit de l'agent de réaction.
PCT/CN2008/071388 2007-07-11 2008-06-20 Procédé de protection d'un catalyseur utilisé pour la préparation d'un ester gras inférieur Ceased WO2009006815A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CNB200710201053XA CN100432039C (zh) 2007-07-11 2007-07-11 一种保护制备低级脂肪酸酯所用酸性离子交换树脂催化剂方法
CN200710201053.X 2007-07-11

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WO2009006815A1 true WO2009006815A1 (fr) 2009-01-15

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112745897A (zh) * 2019-10-30 2021-05-04 中国石油化工股份有限公司 一种提高催化剂利用率的异丁烯叠合方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100432039C (zh) * 2007-07-11 2008-11-12 胡先念 一种保护制备低级脂肪酸酯所用酸性离子交换树脂催化剂方法
CN101560152B (zh) * 2009-05-27 2012-05-23 南京工业大学 一种合成丙酸酯的方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0601929A1 (fr) * 1992-12-08 1994-06-15 Daicel Chemical Industries, Ltd. Procédé de préparation de l'acétate d'isopropyle
US5457228A (en) * 1990-10-31 1995-10-10 Daicel Chemical Industries, Ltd. Method for producing lower alkyl acetate
CN1309629A (zh) * 1998-07-14 2001-08-22 英国石油化学品有限公司 酯合成
CN1483717A (zh) * 2003-06-13 2004-03-24 华南理工大学 乙酸异丙酯的合成工艺及其催化剂的制备方法
CN101081812A (zh) * 2007-07-11 2007-12-05 胡先念 一种保护制备低级脂肪酸酯所用酸性离子交换树脂催化剂方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5457228A (en) * 1990-10-31 1995-10-10 Daicel Chemical Industries, Ltd. Method for producing lower alkyl acetate
EP0601929A1 (fr) * 1992-12-08 1994-06-15 Daicel Chemical Industries, Ltd. Procédé de préparation de l'acétate d'isopropyle
CN1309629A (zh) * 1998-07-14 2001-08-22 英国石油化学品有限公司 酯合成
CN1483717A (zh) * 2003-06-13 2004-03-24 华南理工大学 乙酸异丙酯的合成工艺及其催化剂的制备方法
CN101081812A (zh) * 2007-07-11 2007-12-05 胡先念 一种保护制备低级脂肪酸酯所用酸性离子交换树脂催化剂方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112745897A (zh) * 2019-10-30 2021-05-04 中国石油化工股份有限公司 一种提高催化剂利用率的异丁烯叠合方法

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CN100432039C (zh) 2008-11-12

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