Research Progress on the Synthesis of Organic Peroxide in Microreactor

doi:10.19894/j.issn.1000-0518.240183

Chinese Journal of Applied Chemistry ›› 2024, Vol. 41 ›› Issue (11): 1535-1551.DOI: 10.19894/j.issn.1000-0518.240183

• Review •

Research Progress on the Synthesis of Organic Peroxide in Microreactor

Hui-Lin YI()

State Key Laboratory of Chemical Safety，SINOPEC Research Institute of Safety Engineering Co. ，Ltd. ，Qingdao 266000，China

Received:2024-06-12 Accepted:2024-10-13 Published:2024-11-01 Online:2024-12-04
Contact: Hui-Lin YI
About author:yihl.qday@sinopec.com
Supported by:
the National Natural Science Foundation of China(22278452)

Abstract

Abstract:

Organic peroxides are widely used chemical additives as polymerization initiators， polyester curing agents， crosslinking agents for polymer materials， and oxidants. The traditional synthesis process within batch reactor has low phase transfer rate， uncontrollable process parameters， large liquid hold-up， leading to low efficiency， poor quality， and high risk. Microreaction systems have unique advantages for peroxidation process due to their large specific surface area， enhanced mass and heat transfer rates， and high controllability. This article reviews the research progress on the synthesis of organic peroxides in microreactors in the past decadefrom the perspective of the general and specific challenges lying in the synthesis of organic peroxide acid， peroxyesters， alkyl hydroperoxide， and ketone peroxide. It introduces the commonly used reaction systems， operating parameters， and microreactor types for the synthesis of organic peroxides， discusses the important role and potential problems of microreactors in improving the controllability， efficiency， and safety in peroxidation reaction. Finally， the solutions and future development trends for the improvement of peroxidation in micro-scale are proposed.

Key words: Organic peroxide, Continuous synthesis, Microreactor, Process intensification

CLC Number:

O622.3

Hui-Lin YI. Research Progress on the Synthesis of Organic Peroxide in Microreactor[J]. Chinese Journal of Applied Chemistry, 2024, 41(11): 1535-1551.

Figures/Tables 16

Fig.1 The structure of slit interdigital micromixer［21］：（A） Microreactor in laboratory scale；（B） Conceptual model of microreactor in industrial scale

Fig.2 The production of PFA and PAA in capillary microreactor［22］：（A） Schematic diagram of microreaction system；（B） Comparison between data obtained by model and experiment；（C） Comparison of different models in predicting kinetic parameters （blue dots-advection flow model， others-laminar flow models with different parameters）

Fig.3 The production of PFA and PAA in microreactor with different structures：（A） AFR （A1.image of microreaction system； A2.the structure of microreactor）［23］；（B） Spiral capillary microreactor［24］；（C） Microreactor for dispersion enhancement （C1 and C2 represent the schematic diagram of microreaction system and microreactor， respectively）［25］

Fig.4 New flowsheet for PAA and penicillin G sulfoxide synthesis and separation［28］

Fig.5 Scaling-out of the PFA-mediated oxidation of 3-phenylpropionaldehyde［29］

Fig.6 Production of organic peroxide acid in a fixed bed microreactor using heterogeneous catalyst［32-34］：（A） Preparation of PFA catalyzed by Dowex 50Wx8 （A1.morphology of catalyst； A2.schematic diagram of microreaction system； A3.comparison of catalyst effect between Dowex 50Wx8 and sulfuric acid）；（B） Infrared spectroscopy characterization of heterogeneous catalyst （B1.Amberlite IR 120 Na； B2.Amberlyst 15）

Table 1 Summary and comparison of organic peroxide acid synthesis

Target product	Microreactor type	Reaction condition			Product		Ref.
Target product	Microreactor type	Catalyst	Temperature/K	Residence time/min	Conversion/%	Concentration	Ref.
PFA	Slit interdigital micromixer	Sulfuric acid with mass fraction of 96% （mass fraction of 6% for the total reaction system）	313	4	/	13% （mass fraction）	［21］
	Advanced-flow reactor	Sulfuric acid with mass fraction of 98% （mass fraction of 1% for the total reaction system）	303	1	95.85	6.25 mol/L	［23］
	Capillary	Sulfuric acid with mass fraction of 98% （mole fraction accounts for 4% of FA dosage）	303	6	72.78	5.175 mol/L	［24］
	Fixed bed with ultrasonic	Amberlite IR-120H	313	10	79.59	3.55 mol/L	［38］
PAA	Slit interdigital micromixer	Sulfuric acid with mass fraction of 96% （mass fraction of 6% for the total reaction system）	343	10	/	23% （mass fraction）	［21］
	Serpentine	Sulfuric acid with mass fraction of 98% （mole fraction of 6% for the total reaction system）	333	9	40	/	［26］
	capillary			9	58	3.751 mol/L
	AFR			9	56	/
	Capillary	Sulfuric acid with mass fraction of 98% （1.2 mol/L）	343	3.3	50	30% （mass fraction）	［28］
	Fixed bed	Dowex 50 Wx8	423	10	79.59	3.55 mol/L	［32］
	Fixed bed with ultrasonic	Amberlite IR-120H	413	10	92	5.125 mol/L	［39］
PBA	Capillary	Sulfuric acid with mass fraction of 97% （mole fraction of 10% for the total reaction system）	423	10	72.36	4.0375 mol/L	［27］
PBA	Fixed bed	Amberlyst15	463	8	56.2	2.9 mol/L	［34］

Fig.7 Production of TBHP by gas-liquid oxidation of isobutane：（A） Comparison of TBHP and DTBP as initiator［41］；（B） Image of microreaction system［42］

Fig.8 Non-catalyzed oxidation of isopropylbenzene in different microreactors［44］：（A） Schematic diagram of microreaction system；（B） Membrane dispersed microreactor；（C） Spiral capillary microreactor；（D） Stirred tank reactor

Fig.9 Reaction equations for the synthesis of peroxyester［51］

Fig.10 Process and microreactor development of TBPP synthesis：（a） Study on the reaction process of KTBP and PivCl （a1. The schematic diagram of experimental device； a2. Dispersion process of two phases）［51］；（b） Schematic diagram of development steps for microreactor［52］

Fig.11 Production of TBPEH in microreactor［55］：（A） The schematic diagram of microreaction system；（B） The dispersion process of squeezing flow；（C） The speculation of reaction mechanism

Fig.12 Reaction equations of MEKPO synthesis［57］

Fig.13 Configuration of the microreaction system and T-mixer［57］

Fig.14 Production of MEKPO in capillary microreactor：（A） Microreaction system in laboratory scale［59］；（B） Pilot plant with scale of thousand ton/year［60］

Table 2 Summary and comparison of organic peroxides synthesis in different microreactors

Microreactor type	Target product	Commercialized or not	Advantages	Disadvantages	Ref.
Slit interdigital micromixer	PFA，PAA	Yes	High mixing efficiency	High cost	［21］
AFR	PFA，PAA，TBHP	Yes	High mixing efficiency	High cost	［23，26］
Capillary	PFA，PAA，PBA，TBHP，CHP，TBPP，TBPEH，MEKPO	No	Low cost， easy to operate	Restricted size limit to ensure the mixing effect， large pressure drop	［24，26-28，42，44-45，52，55-56，58-60］
Fixed bed	PFA	No	Low cost， easy to operate	Low activity of heterogenous catalysts	［32，34，38］
Membrane dispersion	CHP	No	Large interfacial area	Large pressure drop， the core membrane components are prone to wear and tear	［45］
Orifice	TBPP，TBPEH	No	Suitable for heterogeneous reaction	Large pressure drop	［53-55］
Split & converge	TBPP，TBPEH	No	Suitable for heterogeneous reaction	Complex structure， high requirements for machining accuracy	［55］

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[1]	Yi-Cheng ZHANG, Fei ZHA, Xiao-Hua TANG, Yue CHANG, Hai-Feng TIAN, Xiao-Jun GUO. Research Progress of Heterogeneous Catalytic Preparation of Organic Peroxides [J]. Chinese Journal of Applied Chemistry, 2023, 40(6): 769-788.
[2]	HE Wei1, FANG Zheng1, CHEN Ketao2, WANG Zhidong1, GUO Kai3*. Application of Microreactor Technology in Synthetic Chemistry [J]. Chinese Journal of Applied Chemistry, 2013, 30(12): 1375-1385.

Research Progress on the Synthesis of Organic Peroxide in Microreactor

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