CN112452345B - Catalyst for gas phase fluorination synthesis of trans-1-chloro-3, 3-trifluoropropene and synthesis method thereof - Google Patents

Catalyst for gas phase fluorination synthesis of trans-1-chloro-3, 3-trifluoropropene and synthesis method thereof Download PDF

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CN112452345B
CN112452345B CN202011285931.2A CN202011285931A CN112452345B CN 112452345 B CN112452345 B CN 112452345B CN 202011285931 A CN202011285931 A CN 202011285931A CN 112452345 B CN112452345 B CN 112452345B
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CN112452345A (en
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吕剑
贾兆华
毛伟
王博
秦越
白彦波
田松
韩升
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Xian Modern Chemistry Research Institute
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Abstract

The invention discloses a catalyst for synthesizing trans-1-chloro-3, 3-trifluoropropene by gas phase fluorination and a synthesis method thereof. The catalyst is prepared from active component M and carrier MgF 2 Composition wherein the active component M is selected from Co 3+ 、Ni 2+ 、Fe 3+ 、Zn 2+ 、La 3+ 、Al 3+ 、Ga 3+ 、Mn 4+ And Cu 2+ The mass of the active component accounts for 5-20% of the total mass of the catalyst. The synthesis method disclosed is to synthesize trans-1-chloro-3, 3-trifluoropropene from HCC-240fa and hydrogen fluoride by gas phase fluorination, and the catalyst is the catalyst of the invention. The catalyst of the invention has better service life and higher catalytic activity, and the catalyst can continuously run for 1000h in the reaction of synthesizing E-HCFO-1233zd by gas-phase catalysis of HCC-240fa through one-step fluorination with high selectivity, and the conversion rate of HCC-240fa is more than 99 percent.

Description

Catalyst for gas phase fluorination synthesis of trans-1-chloro-3, 3-trifluoropropene and synthesis method thereof
Technical Field
The invention relates to a catalyst, in particular to an environment-friendly catalyst for synthesizing trans-1-chloro-3, 3-trifluoropropene by gas-phase catalysis of 1, 3-pentachloropropane through one-step fluorination with high selectivity.
Background
In recent years, researches show that PU rigid foam synthesized by adopting a trans-1-chloro-3, 3-trifluoropropene (E-HCFO-1233 zd) foaming system has good comprehensive performance and excellent heat insulation performance, and can meet the requirements of heat insulation industry. More importantly, the ODP of E-HCFO-1233zd is only 0.00024, the GWP is only 5.0, the toxicity is low, the material is incombustible in normal state, and the material is safe to use, so the material is recognized as the latest generation of environment-friendly fluorine-containing foaming agent. In addition, the E-HCFO-1233zd can be used as working medium of high-temperature heat pump, refrigerant of centrifugal machine, solvent and fluorine-containing intermediate.
In recent years, the synthesis technology of E-HCFO-1233zd has become one of the most active research subjects in the fluorine chemical industry at home and abroad. There are over ten reported synthetic routes to E-HCFO-1233zd, starting materials are 1,1,1,3,3-pentachloropropane (HCC-240 fa), 1,1,3,3-tetrachloro-2-propene, 1,1,1,2,3,3-hexachloropropane, 1,1,1-trifluoro-2,3-dichloropropane, 1,1,1,3,3-pentafluoropropane, 1,1,1,3-tetrafluoropropene, chlorotrifluoropropene, trifluoromethane and the like. The synthesis route adopted in the actual industrial production mainly takes HCC-240fa as the raw material and anhydrous hydrogen fluoride as the fluorine source to synthesize the E-HCFO-1233zd through liquid phase or gas phase fluorination reaction by comprehensively considering the factors of raw material sources, production process, three wastes and the like.
Chinese patent CN107652160 uses TiCl 4 The composition of KF and KF is used as catalyst, the reaction temperature range is 80-130 deg.C, and the liquid phase reaction pressure is 1.25-2.0 MPa. At present, the E-HCFO-1233zd synthesized by adopting a liquid phase fluorination method has the problems of poor catalyst stability and difficult recycling, and the process equipment has serious corrosion, more three wastes and great pollution. The vapor phase method is Cr 2 O 3 /Al 2 O 3 As a catalyst, HCC-240fa reacts with hydrogen fluoride in a gas phase at a temperature of between 150 and 300 ℃ to generate E-HCFO-1233zd. The gas phase method has the advantages of small pollution, high yield and easy continuous production, and is the most promising industrialized process. However, since chromium is a carcinogen with strong toxicity, the potential chromium pollution caused thereby is a departure from environmental friendliness, which places great environmental pressure on the entire industrial chain. In addition, the chromium-based catalyst has strong surface acidity, poor selectivity in the reaction of synthesizing E-HCFO-1233zd, and is very easy to deposit carbon and deactivate.
Disclosure of Invention
Aiming at the problems and the defects in the prior art, the invention firstly provides a catalyst for synthesizing trans-1-chloro-3, 3-trifluoropropene by gas-phase fluorination.
For this purpose, the catalyst provided by the invention consists of an active component M and a carrier MgF 2 Composition wherein the active component M is selected from Co 3+ 、Ni 2+ 、Fe 3+ 、Zn 2+ 、La 3+ 、Al 3+ 、Ga 3+ 、Mn 4+ And Cu 2+ The mass of the active component accounts for 5-20% of the total mass of the catalyst.
Further, the carrier MgF 2 Has rutile phase, nano structure, and specific surface area greater than 120m 2 Sintering resistance at 500 ℃ or below.
Optionally, M is selected from Fe 3+ And Al 3+ Combinations of (a) and (b). Further optionally, the Fe 3+ With Al 3+ The molar ratio of (a) to (b) is 5.
Meanwhile, the invention provides a preparation method of the catalyst. For this purpose, the preparation method comprises the following steps:
(1) Preparing MgF by reacting polyhydric alcohol solution of magnesium salt with fluorinating reagent at 150-240 DEG C 2 A carrier; the magnesium salt is selected from one of magnesium nitrate, magnesium chloride, magnesium sulfate, magnesium methoxide, magnesium ethoxide and magnesium acetate; the polyol is one or more of ethylene glycol, propylene glycol, glycerin and diol; the fluorinating reagent is selected from aqueous solution of hydrogen fluoride, alcoholic solution of hydrogen fluoride or ether solution of hydrogen fluoride;
(2) Loading a salt solution containing M to MgF by stepwise impregnation, by equal volume impregnation or by co-impregnation 2 Carrying out roasting treatment on the carrier at 300-500 ℃ after aging to obtain a catalyst precursor; the M-containing salt is selected from one or a combination of more than two of nitrate, chloride and sulfate;
(3) Fluorinating the catalyst precursor at 150-400 ℃ to obtain M/MgF 2 A catalyst; the fluorinating agent used in the fluorination treatment is selected from hydrogen fluoride, dichlorodifluoromethane, chlorodifluoromethane or chlorotrifluoromethane.
Optionally, mg in the step (1) 2+ The molar ratio to hydrogen fluoride is 1.
Further, the present invention provides a method for synthesizing trans-1-chloro-3, 3-trifluoropropene. The provided method takes HCC-240fa and hydrogen fluoride as raw materials to synthesize trans-1-chloro-3, 3-trifluoropropene by a gas phase fluorination method, and the catalyst used in the gas phase fluorination method is the catalyst.
Alternatively, in the synthesis method of trans-1-chloro-3, 3-trifluoropropene according to the present invention, the reaction temperature is 200-260 ℃, the contact time of the reaction mass with the catalyst is 4-20s, and the molar ratio of hydrogen fluoride to HCC-240fa is in the range of (5-40): 1.
Compared with the prior art, the catalyst has larger specific surface area and anti-sintering performance, and the specific surface area of the magnesium fluoride carrier after being roasted at 400 ℃ is more than 120m 2 Per g, the specific surface area is more than 250m after doping active components 2 (ii)/g; the catalyst has better service life and higher catalytic activity, and continuously operates 1000h in the reaction of synthesizing E-HCFO-1233zd by one-step fluorination and high selectivity by catalyzing HCC-240fa in a gas phase, and the conversion rate of HCC-240fa is more than 99 percent; at the same time, the selectivity of E-HCFO-1233zd is maintained to be more than 90.0 percent, and the E/Z ratio is more than 12.
Drawings
FIG. 1 is the MgF prepared in example 2 2 X-ray powder diffraction pattern of the support;
FIG. 2 shows MgF in the catalyst prepared in example 2 2 High power transmission electron micrograph of the support;
FIG. 3 shows that MgF in the catalyst obtained by different calcination temperatures in example 2 2 N of the vector 2 Adsorption and desorption isothermal curves and corresponding specific surface areas;
FIG. 4 shows Al-Fe/MgF obtained in example 3 2 N of catalyst 2 Adsorption and desorption isotherm curves and corresponding specific surface areas.
Detailed Description
Unless otherwise indicated, the terms herein are to be understood in accordance with the conventional wisdom of those skilled in the relevant art.
Specific examples of the present invention are given below, but the scope of the present invention is not limited thereto.
The reagents, reaction materials, and equipment used in the following examples are commercially available products.
Example 1:
128g of Mg (NO) 3 ) 2 ·6H 2 Dissolving O in 500ml of glycol solution, dropwise adding 50g of hydrofluoric acid aqueous solution (40 wt%) at 180 ℃, and continuously stirring for 10 hours after dropwise adding is finished to obtain an MgF2 carrier;
aging magnesium fluoride carrier at normal temperature for 10h, and roasting at 400 ℃ for 5h to obtain MgF 2 A precursor; finally, mgF is treated at 400 DEG C 2 The precursor is fluorinated in hydrogen fluoride atmosphere to obtain MgF 2 A catalyst.
Taking MgF 2 And (2) transferring 20mL of catalyst into a fixed bed tubular reactor, heating to 260 ℃, drying for 2h, introducing hydrogen fluoride gas, then introducing HCC-240fa, wherein the molar ratio of hydrogen fluoride to HCC-240fa is 5, the contact time is 20s, after 12h, absorbing hydrogen fluoride and hydrogen chloride by water, KOH or NaOH alkali, and then feeding the products into a gas chromatograph for analysis, and calculating the conversion rate of HCC-240fa and the selectivity of a target product E-HCFO-1233zd by adopting an area normalization method. The HCC-240fa conversion was 89.5%, the selectivity to E-HCFO-1233zd was 82.0%, the selectivity to Z-HCFO-1233zd was 11.4%, and the E/Z ratio was 7.2, as analyzed.
Example 2:
128g of Mg (NO) 3 ) 2 ·6H 2 Dissolving O in 500ml of propylene glycol solution, dropwise adding 50g of hydrofluoric acid ether solution (40 wt%) at 150 ℃, and continuously stirring for 12 hours after dropwise adding is finished to obtain an MgF2 carrier;
10.0g of Fe (NO) 3 ) 3 ·9H 2 Dissolving O in deionized water to obtain soaking solution, and soaking the solution in the same volume to 90.0g MgF 2 On a carrier, aging at normal temperature for 8h, and then roasting at corresponding temperature for 5h to obtain Fe/MgF 2 A precursor; finally, fe/MgF is treated at 150 DEG C 2 The precursor is fluorinated in hydrogen fluoride atmosphere to obtain Fe/MgF 2 A catalyst; mgF in the obtained catalyst 2 The carrier has rutile phase (shown in figure 1) and nano-spherical structure (shown in figure 2), and specific surface area greater than 120m 2 (g) and is superior in sintering resistance at 500 ℃ (see FIG. 3, which shows the corresponding firing temperature).
Taking Fe/MgF 2 20mL of catalyst is transferred into a fixed bed tubeHeating to 245 ℃ in a reactor, drying for 2h, introducing hydrogen fluoride gas, then introducing HCC-240fa, wherein the molar ratio of hydrogen fluoride to HCC-240fa is 25, the contact time is 12s, after 12h, absorbing hydrogen fluoride and hydrogen chloride by water, KOH or NaOH alkali, and then analyzing by a gas chromatograph, and calculating the conversion rate of HCC-240fa and the selectivity of a target product E-HCFO-1233zd by adopting an area normalization method. The HCC-240fa conversion was 99.9%, the selectivity to E-HCFO-1233zd was 99.9%, the selectivity to Z-HCFO-1233zd was 9.4%, and the E/Z ratio was 9.5, as analyzed.
Example 3:
128g of Mg (NO) 3 ) 2 ·6H 2 Dissolving O in 500ml of a diol solution, dropwise adding 50g of hydrofluoric acid alcohol solution (40 wt%) at 240 ℃, and continuously stirring for 6 hours after dropwise adding is finished to obtain an MgF2 carrier;
10.0g of Fe (NO) 3 ) 3 ·9H 2 O、3.0g Al(NO 3 ) 3 ·9H 2 Dissolving O in deionized water to obtain soaking solution, and soaking the solution in the same volume to obtain MgF 2 On a carrier, aging at normal temperature for 12h, and then roasting at 400 ℃ for 5h to obtain Al-Fe/MgF 2 A precursor; finally, the Al-Fe/MgF is treated at 400 DEG C 2 The precursor is fluorinated in hydrogen fluoride atmosphere to obtain Al-Fe/MgF 2 A catalyst. The specific surface of the prepared catalyst is more than 250m 2 In particular, see FIG. 4.
Taking Al-Fe/MgF 2 And (2) transferring 20mL of catalyst into a fixed bed tubular reactor, heating to 200 ℃, drying for 2h, introducing hydrogen fluoride gas, then introducing HCC-240fa, wherein the molar ratio of hydrogen fluoride to HCC-240fa is 40, the contact time is 4s, after 12h, absorbing hydrogen fluoride and hydrogen chloride by water, KOH or NaOH alkali, and then feeding the products into a gas chromatograph for analysis, and calculating the conversion rate of HCC-240fa and the selectivity of a target product E-HCFO-1233zd by adopting an area normalization method. The conversion of HCC-240fa was 100%, the selectivity to E-HCFO-1233zd was 91.2%, the selectivity to Z-HCFO-1233zd was 7.5%, and the E/Z ratio was 12.2, as analyzed.
Example 4:
based on example 4, A prepared in example 3 was usedl-Fe/MgF 2 The catalyst is used for carrying out reactions for different durations, and the corresponding effects are shown in the table 1.
TABLE 1 Life test
Figure BDA0002782393260000061

Claims (4)

1. A process for synthesizing trans-1-chloro-3, 3-trifluoropropene from HCC-240fa and hydrogen fluoride by gas-phase fluorination features that the catalyst used in gas-phase fluorination process is composed of active component M and MgF as carrier 2 Wherein the active component M is selected from Fe 3+ Or Fe 3+ And Al 3+ The mass of the active component accounts for 5 to 20 percent of the total mass of the catalyst;
the carrier MgF 2 Has rutile phase, nano structure, and specific surface area greater than 120m 2 Per gram, sintering resistance below 500 ℃;
the synthesis method of the catalyst comprises the following steps:
(1) Preparing MgF by reacting polyhydric alcohol solution of magnesium salt with fluorinating agent at 150-240 DEG C 2 A carrier;
the magnesium salt is selected from one of magnesium nitrate, magnesium chloride, magnesium sulfate, magnesium methoxide, magnesium ethoxide and magnesium acetate;
the polyol is one or more of ethylene glycol, propylene glycol, glycerol and diethylene glycol;
the fluorinating reagent is selected from aqueous solution of hydrogen fluoride, alcoholic solution of hydrogen fluoride or ether solution of hydrogen fluoride;
(2) Loading a salt solution containing M to MgF by stepwise impregnation, by equal volume impregnation or by co-impregnation 2 Carrying out roasting treatment on the carrier at 300-500 ℃ after aging to obtain a catalyst precursor; the M-containing salt is selected from one or a combination of more than two of nitrate, chloride and sulfate;
(3) Fluorinating the catalyst precursor at 150-400 ℃ to obtain M/MgF 2 A catalyst;the fluorinating agent used in the fluorination treatment is selected from hydrogen fluoride, dichlorodifluoromethane, chlorodifluoromethane or chlorotrifluoromethane.
2. The method of synthesizing trans-1-chloro-3, 3-trifluoropropene of claim 1, wherein the Fe is 3+ With Al 3+ The molar ratio of (a) to (b) is 5.
3. The process for the synthesis of trans-1-chloro-3, 3-trifluoropropene according to claim 1, wherein in step (1) Mg 2+ The molar ratio of the fluorine-containing compound to the hydrogen fluoride is 1 (3-12).
4. The process for the synthesis of trans-1-chloro-3, 3-trifluoropropene according to claim 1, wherein the reaction temperature is 200-260 ℃, the contact time of the reaction mass with the catalyst is 4-20s, and the molar ratio of hydrogen fluoride to HCC-240fa is in the range of (5-40): 1.
CN202011285931.2A 2020-11-17 2020-11-17 Catalyst for gas phase fluorination synthesis of trans-1-chloro-3, 3-trifluoropropene and synthesis method thereof Active CN112452345B (en)

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Citations (1)

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CN103476736A (en) * 2011-04-25 2013-12-25 霍尼韦尔国际公司 Integrated process to co-produce 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene and trans-1,3,3,3-tetrafluoropropene

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JP4257424B2 (en) * 2004-03-09 2009-04-22 独立行政法人産業技術総合研究所 Catalyst for fluorination reaction
US8704017B2 (en) * 2010-09-03 2014-04-22 Honeywell International Inc. Continuous low-temperature process to produce trans-1-chloro-3,3,3-trifluoropropene
CN104710272B (en) * 2013-12-12 2016-05-25 西安近代化学研究所 A kind of preparation method of 1-chloro-3,3,3 ,-trifluoropropene
CN105107533B (en) * 2015-08-18 2019-04-09 巨化集团技术中心 A kind of preparation method of vapor phase dehydrofluorination catalysts
FR3047240B1 (en) * 2016-01-28 2019-09-27 Arkema France PROCESS FOR THE PRODUCTION OF 2-CHLORO-3,3,3-TRIFLUOROPROPENE
CN109746006A (en) * 2018-12-20 2019-05-14 西安近代化学研究所 Gas phase dehydrofluorination synthesizes 1,3,3,3- tetrafluoropropene with long-life, environmental protection catalyst

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CN103476736A (en) * 2011-04-25 2013-12-25 霍尼韦尔国际公司 Integrated process to co-produce 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene and trans-1,3,3,3-tetrafluoropropene

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