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CN-122010693-A - Method for co-producing diethylene glycol and derivatives thereof and triethylene glycol and derivatives thereof

CN122010693ACN 122010693 ACN122010693 ACN 122010693ACN-122010693-A

Abstract

The invention relates to a method for co-producing diethylene glycol and derivatives thereof and triethylene glycol and derivatives thereof. The method comprises the steps of carrying out contact reaction on ethylene oxide and derivatives thereof and ethylene glycol in the presence of a styrene copolymer, wherein the styrene copolymer is modified by a cyclic quaternary ammonium salt and has a structure shown in the following formula (1): Is a styrene copolymer matrix, R is an alkylene chain, R 1 is an alkylene chain, R 2 is an alkyl group, X ‑ is an anion, and R and N together form a 5-10 membered aliphatic heterocyclic ring. According to the method disclosed by the invention, the ethylene oxide and the derivatives thereof have excellent conversion rate, the polyethylene glycol selectivity is high, and the co-production of diethylene glycol and the derivatives thereof and triethylene glycol and the derivatives thereof can be realized.

Inventors

  • YU FENGPING
  • GE JUNWEI
  • JIN MING
  • ZHOU JIPENG
  • WANG YI
  • HE WENJUN

Assignees

  • 中国石油化工股份有限公司
  • 中石化（上海）石油化工研究院有限公司

Dates

Publication Date
20260512
Application Date
20241111

Claims (10)

  1. 1. A method for co-producing diethylene glycol and derivatives thereof and triethylene glycol and derivatives thereof is characterized by comprising the steps of carrying out contact reaction on ethylene oxide and derivatives thereof and ethylene glycol in the presence of a styrene copolymer; The styrene copolymer is modified by cyclic quaternary ammonium salt and has a structure shown in the following formula (1): In the formula (1), the components are as follows, Is a styrene copolymer matrix, R is an alkylene chain, R 1 is an alkylene chain, R 2 is an alkyl group, X - is an anion, and R and N together form a 5-10 membered aliphatic heterocyclic ring.
  2. 2. The method of claim 1, wherein R and N in formula (1) together form a 6-8 membered aliphatic heterocyclic ring.
  3. 3. The method according to claim 1 or 2, wherein the styrenic copolymer matrix is a gel-type styrene-crosslinker copolymer matrix, preferably, The gel-type styrene-crosslinking agent copolymer matrix has a crosslinking degree of 1-15%, and/or In the styrene copolymer, the mass ratio of the styrene copolymer matrix is 30-60wt%, preferably 30-50wt%.
  4. 4. A process according to any one of claims 1 to 3, wherein the cross-linking agent in the styrenic copolymer matrix is a di-and/or poly-alkenylbenzene and/or a poly-unsaturated acid alcohol ester, preferably a di-and/or poly-alkenylbenzene.
  5. 5. The method according to any one of claims 1 to 4, wherein in the formula (1), R is a C1-C10 linear or branched alkylene chain, preferably a C2-C5 linear or branched alkylene chain, and/or R 1 is a C2-C10 linear or branched alkylene chain, preferably a C3-C6 linear or branched alkylene chain, and/or R 2 is a C1-C6 linear or branched alkyl radical, and/or X-is at least one selected from bicarbonate ion, hydroxide ion, bisulfide ion and organic acid radical ion.
  6. 6. The method according to any one of claims 1 to 5, wherein, The contact reaction is carried out in a fixed bed reactor, and/or The catalyst is packed in the reactor in at least three beds, and/or The average particle size of the catalyst packed in each bed in the reactor is increased layer by layer in the flow direction of the ethylene oxide by an amount of 0.1 to 0.5 mm/layer.
  7. 7. The method according to any one of claims 1 to 6, wherein the method for producing the styrenic copolymer comprises the steps of: (a) Preparing a saturated aliphatic nitrogen heterocycle functionalized styrene copolymer matrix; (b) And (c) sequentially carrying out an ammonification reaction and an ion exchange reaction on the saturated aliphatic nitrogen heterocycle functionalized styrene copolymer matrix prepared in the step (a).
  8. 8. The process according to claim 7, wherein the step (a) is carried out by copolymerizing 4-vinylphenylalkylazacycloalkane with a crosslinking agent as a comonomer in the presence of an initiator, Preferably, in the copolymerization reaction, The mass ratio of the 4-vinylphenyl alkyl azacycloalkane to the cross-linking agent is 85-99:1-15, and/or The mass ratio of the cross-linking agent to the initiator is 1-15:0.1-5.
  9. 9. The method of claim 7, wherein, The conditions for the amination reaction include a temperature of 40-90 ℃, preferably 50-80 ℃, and/or a time of 10-48 hours, preferably 15-30 hours, and/or The ammonification reagent is halogenated C1-C6 alkane, preferably one or more selected from bromoethane, chloropropane, bromobutane, bromopentane, bromohexane, chloroethane, chloropropane, chlorobutane, chloropentane, chlorohexane, iodoethane, iodopropane, iodobutane, iodopentane and iodohexane; And/or The conditions of the ion exchange reaction include a temperature of 25-40 ℃ and/or a time of 5-12 hours.
  10. 10. The method of any one of claims 1-9, wherein the contacting reaction conditions comprise: The reaction temperature is 40-180 ℃, preferably 90-120 ℃, and/or The reaction pressure is 0.1-10.0MPa, preferably 0.8-2.5MPa, and/or, The molar ratio of ethylene glycol to ethylene oxide and its derivatives is (1-50): 1, preferably (3-8): 1, and/or The liquid space velocity is 0.1-6.0h -1 , preferably 0.5-2.0h -1 .

Description

Method for co-producing diethylene glycol and derivatives thereof and triethylene glycol and derivatives thereof Technical Field The invention relates to a method for co-producing diethylene glycol and derivatives thereof and triethylene glycol and derivatives thereof. Background Polyethylene glycol includes diethylene glycol (DEG), triethylene glycol (TEG), tetraethylene glycol (TTEG), and the like, and has wide application. Diethylene glycol, for example, is a colorless, odorless, transparent, hygroscopic, viscous liquid with chemical properties similar to Ethylene Glycol (EG). Diethylene glycol can be directly used as solvent such as nitrocellulose, resin, grease, printing ink and the like, natural gas dehydration desiccant, aromatic separation extractant, textile lubricant, softener and finishing agent, can also be used as antifreezing agent component in brake fluid and compressor lubricating oil, and can also be used for preparing cleaning agent. Triethylene glycol has wide application in industries such as medicine, paint, textile, printing and dyeing, food, paper making, cosmetics, leather making, photography, printing, metal processing and the like, and can be used as a solvent for extracting aromatic hydrocarbon, a solvent for rubber and nitrocellulose, a diesel additive and rocket fuel. Diethylene glycol and triethylene glycol are by-products in the process of producing ethylene glycol by an ethylene oxide hydration method, the yield of the diethylene glycol and the triethylene glycol is limited by the operation condition of an ethylene glycol device, and the molar ratio of main products in general industrial production is approximately EG: DEG: TEG=100:10:1. The current ethylene oxide/ethylene glycol production technology is mature, and the technology is mainly provided by DOW, SD, SHELL and other large chemical enterprises. The main process is that ethylene oxide and excessive water react in a tubular reactor at 150-200 ℃ and 1.5-2.5MPa, ethylene glycol is prepared by direct liquid phase hydration, and meanwhile, diethylene glycol, triethylene glycol and polyethylene glycol are byproducts. And cooling the ethylene glycol solution obtained by the reaction through a heat exchanger, then pumping the ethylene glycol solution to evaporate and concentrate, and obtaining pure ethylene glycol, diethylene glycol, triethylene glycol and other components respectively after multi-effect evaporation. CN115991634a discloses a process for producing triethylene glycol, in which ethylene oxide and diethylene glycol are mixed by a static mixer and then heated to react to produce triethylene glycol. Can be used for the transformation of the existing EO/EG device, can obviously increase the amount of the byproduct triethylene glycol, has simple preparation process and high yield, and can be flexibly produced according to market change. It can be seen that the production of polyethylene glycol (e.g., diethylene glycol, triethylene glycol, etc.) is currently limited by the capacity of EOEG units. Disclosure of Invention The invention aims to solve the problem of low production efficiency of polyethylene glycol in the prior art, and provides a method for co-producing diethylene glycol and derivatives thereof and triethylene glycol and derivatives thereof. In order to achieve the above object, the present invention provides a method for co-producing diethylene glycol and its derivatives and triethylene glycol and its derivatives, comprising the steps of subjecting ethylene oxide and its derivatives to a contact reaction with ethylene glycol in the presence of a styrenic copolymer; The styrene copolymer is modified by cyclic quaternary ammonium salt and has a structure shown in the following formula (1): Is a styrene copolymer matrix, R is an alkylene chain, R 1 is an alkylene chain, R 2 is an alkyl group, X - is an anion, and R and N together form a 5-10 membered aliphatic heterocyclic ring. Through the technical scheme, the invention has the following advantages: According to the method disclosed by the invention, the ethylene oxide and the derivatives thereof have excellent conversion rate, the polyethylene glycol selectivity is high, and the co-production of diethylene glycol and the derivatives thereof and triethylene glycol and the derivatives thereof can be realized, wherein the selectivity of the triethylene glycol and the derivatives thereof is more than 15%, and the preferable scheme can be more than 20%. Drawings FIG. 1 is an infrared spectrum of ion exchange resin Cat-A1. Detailed Description The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each othe