CN111013612B - Preparation method of solid fluorination catalyst - Google Patents

Preparation method of solid fluorination catalyst Download PDF

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CN111013612B
CN111013612B CN201911325891.7A CN201911325891A CN111013612B CN 111013612 B CN111013612 B CN 111013612B CN 201911325891 A CN201911325891 A CN 201911325891A CN 111013612 B CN111013612 B CN 111013612B
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catalyst
chromium
fluorination
fluorination catalyst
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CN111013612A (en
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丁晨
王鑫
都荣礼
李汉生
王伟
田丁磊
朱辉
牛韦
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Shandong Dongyue Green Cold Technology Co ltd
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    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/22—Halogenating
    • B01J37/26—Fluorinating
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/12—Oxidising
    • B01J37/14—Oxidising with gases containing free oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX

Abstract

The invention provides a preparation method of a solid fluorination catalyst, which comprises the following steps: dissolving a mixture of chromium chloride and chromium nitrate and an auxiliary agent in deionized water to obtain a mixed salt solution; adding the obtained mixed salt solution into a precipitant solution, controlling the pH of the system to precipitate the salt solution, collecting and drying the precipitate, and roasting in different atmospheres in sections to obtain a catalyst precursor; and tabletting and forming the obtained catalyst precursor, and then fluorinating the catalyst precursor by using trifluoromethane to obtain the fluorination catalyst. According to the method, nitrogen oxide generated by decomposition of nitrate during roasting and oxygen in air are utilized to oxidize trivalent chromium to a certain extent, the valence of chromium can be improved, and meanwhile, trifluoromethane is used as a fluorination reagent, so that the problems that hydrogen fluoride reacts violently as a common fluorination reagent, heat release is high, and catalyst sintering is easily caused can be effectively avoided. The catalyst prepared by the method is used for preparing R134a and R125, and has the advantage of high activity.

Description

Preparation method of solid fluorination catalyst
Technical Field
The invention relates to a preparation method of a solid fluorination catalyst, in particular to a catalyst for producing difluoromethane, tetrafluoroethane, pentafluoroethane and tetrafluoropropene products, belonging to the technical field of catalyst preparation.
Background
The chlorofluorocarbon exchange reaction is a key reaction step in the preparation of chlorofluorocarbons. The existing chlorofluorocarbon products mainly depend on solid gas phase fluorination catalysts, and the catalysts used at the present stage are generally chromium-based catalysts taking chromium element as a main active component, and certain catalyst performance is improved by adding auxiliary metals. For example, EP0502605 discloses a method of increasing the catalyst activity by adding Co, ni, zn, or the like as an auxiliary metal.
In the case of fluorination catalysts, the activity of the catalyst is closely related to the structure formed by fluorination of the catalyst and the valence of chromium in the catalyst. Patent document US6433233 teaches that chromium has a valence between 3.5 and 5.0, which contributes to the increase in catalyst activity. US5849658 also discloses that the catalytic activity of the catalyst has a considerable relationship with its surface area, and a higher specific surface area contributes to an increase in the activity of the catalyst.
Many studies show that trivalent chromium fluoride has a small effect on the exchange reaction of fluorine and chlorine, while hexavalent chromium fluoride runs off too fast, and the service life of the catalyst is short. Therefore, in order to ensure the catalytic activity of the chromium-based catalyst, the valence state of the chromium element needs to be strictly regulated and controlled. In the prior art, chlorine or oxygen is generally used for oxidizing the chromium-based catalyst, but the oxidation effect is not ideal and the obtained catalyst has low activity. Therefore, in order to obtain a high valence state chromium-based catalyst, there is a patent report on activating the catalyst with fluorine gas. For example: chinese patent document CN106824232A provides a high-valence chromium-based catalyst, a preparation method and an application, wherein the high-valence chromium-based catalyst consists of high-valence chromium ions and an auxiliary agent, and the method is to prepare the high-valence chromium-based catalyst by roasting a catalyst precursor and activating the catalyst precursor in fluorine gas. However, fluorine gas is a highly dangerous and highly toxic gas, and huge potential safety hazards exist in the transportation, storage and use processes of the fluorine gas. Simultaneously, hydrogen fluoride is chooseed for use to current fluorination reaction reagent, and hydrogen fluoride is difficult to control, and the reaction is violent, causes the catalyst sintering because the reaction is too violent exothermic easily to make the catalyst have the risk that the activity reduces, and hydrogen fluoride has stronger corrosivity, and is great to equipment damage, easily causes the corruption to reveal, and the security is lower.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a solid fluorination catalyst. The preparation method can effectively realize that the chromium element in the chromium-based catalyst has higher valence, simultaneously avoids the problem that the catalyst is easy to sinter in the hydrofluoride fluorination process, and the fluorination catalyst obtained by the invention has higher activity.
The technical scheme of the invention is as follows:
a preparation method of a solid fluorination catalyst comprises the following steps:
(1) Dissolving a mixture of chromium chloride and chromium nitrate and an auxiliary agent in deionized water to obtain a mixed salt solution;
(2) Adding the mixed salt solution obtained in the step (1) into a precipitant solution, controlling the pH value of the system to precipitate the salt solution, collecting and drying the precipitate, and roasting the precipitate in different atmospheres in sections to obtain a catalyst precursor;
(3) And (3) tabletting and forming the catalyst precursor obtained in the step (2), and then fluorinating by using trifluoromethane to obtain the fluorination catalyst.
According to the present invention, it is preferable that the mass ratio of the chromium nitrate to the chromium chloride in the step (1) is 0.1 to 12:1, more preferably 3 to 10:1. the ratio of the chromium nitrate to the chromium chloride is controlled within the range, so that the valence state of chromium can be ensured to be 3-6, and if the content of the chromium nitrate is too high or the chromium nitrate is completely chromium nitrate, the chromium element is over oxidized, the hexavalent chromium is excessive, the loss of the catalyst is easy to cause, and the service life of the catalyst is shortened; meanwhile, if the content of the chromium nitrate is too low, the oxidation degree of the chromium element is low, and the activity of the obtained catalyst is low.
According to the invention, preferably, the assistant in the step (1) is zinc nitrate, and the addition amount of the assistant is 10% of the total mass of the chromium chloride and the chromium nitrate.
According to the invention, preferably, the precipitant solution in step (2) is 5-15% ammonia water by mass;
preferably, the pH value of the system is controlled to be 7-9.
According to the present invention, it is preferable that the drying temperature in the step (2) is 90 to 110 ℃ and the drying time is 5 to 8 hours.
According to the present invention, preferably, the step of the staged firing in the step (2) is: firstly, roasting the dried precipitate for 5-7h at 250-450 ℃ in nitrogen, and then roasting for 5-7h at 300-450 ℃ in mixed gas of air and nitrogen;
further preferably, the volume ratio of air to nitrogen in the mixed gas is 2-10:1.
according to the present invention, preferably, the fluorination step in step (3) is: drying the catalyst precursor subjected to tabletting molding in a nitrogen atmosphere at 300 ℃ for 20-30h, introducing trifluoromethane, fluorinating at 300 ℃ for 80-120h, and naturally cooling to room temperature to obtain a fluorination catalyst;
further preferably, the flow rate of the trifluoromethane is 100-800mL/min, more preferably 200-500mL/min;
more preferably, the fluorination time is 100h.
The invention has the following technical characteristics and beneficial effects:
1. according to the preparation method, chromium nitrate is added into chromium chloride, the chromium hydroxide precipitate obtained by reaction with a precipitator contains nitrate ions, the obtained chromium hydroxide precipitate is firstly roasted in a nitrogen atmosphere, the chromium hydroxide precipitate is fully pyrolyzed to obtain chromium oxide, meanwhile, nitrate is decomposed at high temperature to generate oxynitride, the generated oxynitride has certain oxidability, and the chromium oxide is oxidized to a certain degree; and calcining in the mixed gas of air and nitrogen subsequently, and further oxidizing the chromium element by using oxygen to ensure that the chromium element in the catalyst has higher valence. By H in FIG. 1 2 The TPR curve shows that the catalyst has an obvious low-temperature reduction peak, which indicates that the chromium element in the catalyst has higher valence, thereby improving the catalytic activity of the catalyst.
2. In the preparation method, the proportion of the chromium nitrate and the chromium chloride is strictly controlled, the valence state of the chromium is ensured to be 3-6, and if the content of the chromium nitrate is too high or the chromium nitrate is completely chromium nitrate, the chromium element is over oxidized, the hexavalent chromium is excessive, the loss of the catalyst is easy to cause, and the service life of the catalyst is shortened; if the content of chromium nitrate is too low, the oxidation degree of chromium element is low, and the activity of the obtained catalyst is low.
3. According to the preparation method, trifluoromethane is used for replacing a traditional fluorination reagent HF in the fluorination process, so that the problem that catalyst sintering is possibly caused by excessive violent heat release in fluorination is avoided, the chromium oxyfluoride fluorination catalyst with a certain high valence state is prepared, and the obtained fluorination catalyst has high catalytic activity; meanwhile, the hydrogen fluoride has strong corrosivity, great damage is caused to equipment, and corrosion leakage is easily caused.
Drawings
FIG. 1 is H of the solid fluorination catalyst of example 1 2 -TPR curve.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following specific examples.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
A preparation method of a solid fluorination catalyst comprises the following steps:
dissolving 15g of chromium chloride and 75g of chromium nitrate in 1L of water, adding 9g of zinc nitrate, continuously and uniformly stirring to prepare a mixed salt solution, preparing 170g of ammonia water with the mass fraction of 10% as a precipitator solution, uniformly adding the mixed salt solution into the precipitator solution, controlling the pH value of the system to be 8, filtering and collecting precipitates, and drying at 100 ℃ for 6 hours. The dried precipitate was placed in a tubular muffle furnace at N 2 Roasting for 6h at 300 ℃ in the atmosphere, then roasting for 6h at 300 ℃ in a mixed gas of air and nitrogen, wherein the volume ratio of the air to the nitrogen in the mixed gas is 5:1, obtaining a catalyst precursor, tabletting and forming the catalyst precursor, putting the catalyst precursor into a reaction tube for fluorination, firstly drying for 24h at 300 ℃ in the nitrogen atmosphere, then introducing trifluoromethane (R23) according to the flow of 300mL/min, fluorinating for 100h at 300 ℃, and naturally cooling to room temperature, thus obtaining the fluorination catalyst A.
H of the solid fluorination catalyst prepared in this example 2 The TPR curve is shown in figure 1, and as can be seen from figure 1, the catalyst has a distinct low-temperature reduction peak, which indicates that the chromium element in the catalyst has a higher valence.
Example 2
A solid fluorination catalyst was prepared as described in example 1, except that 75g of chromium chloride and 15g of chromium nitrate were used to obtain fluorination catalyst B.
Example 3
A method of making a solid fluorination catalyst, as described in example 1, except that the volume ratio of air to nitrogen in the mixed gas during calcination was 3:1, gives fluorination catalyst C.
Example 4
A method of making a solid fluorination catalyst was conducted as described in example 1, except that trifluoromethane was controlled to flow 500mL/min to provide fluorination catalyst D.
Example 5
A method of making a solid fluorination catalyst, as in example 2, except that the volume ratio of air to nitrogen in the mixed gas during calcination was 3:1, gives fluorination catalyst E.
Example 6
A method of making a solid fluorination catalyst, as described in example 2, except that trifluoromethane was controlled at 500mL/min, gave fluorination catalyst F.
Comparative example 1
A preparation method of a solid fluorination catalyst comprises the following steps:
dissolving 90g of chromium chloride in 1L of water, adding 9g of zinc nitrate, continuously and uniformly stirring to prepare a mixed salt solution, preparing 185g of ammonia water with the mass fraction of 10% as a precipitator solution, uniformly adding the mixed salt solution into the precipitator solution, controlling the pH value of the system to be 8, filtering, collecting precipitates and drying at 100 ℃ for 6 hours. The dried precipitate was placed in a tubular muffle furnace at N 2 Roasting at 300 deg.C for 6h in atmosphere, and then roasting at 300 deg.C for 6h in mixed gas of air and nitrogen gas with volume ratio of air to nitrogen gas5:1 to obtain a catalyst precursor, tabletting and forming the catalyst precursor, placing the catalyst precursor into a reaction tube for fluorination, drying the catalyst precursor in a nitrogen atmosphere at 300 ℃ for 24 hours, introducing trifluoromethane (R23) according to the flow of 300mL/min, fluorinating the catalyst precursor at 300 ℃ for 100 hours, and naturally cooling the catalyst precursor to room temperature to obtain a fluorination catalyst G.
Test example 1
100mL of the catalysts prepared in examples 1 to 6 and comparative example 1 were charged in 316L,1 meter long DN25 stainless steel tubes, respectively, the catalysts were fixed in the middle, purged with nitrogen gas at 300 ℃ for 4 hours, and then HF and R133a (CF) were introduced into the tubes, respectively 3 CH 2 Cl), controlling the mole ratio of HF to R133a to be 8:1, controlling the reaction temperature to be 350 ℃, carrying out certain reaction under the condition, washing a reaction product by water and alkali to remove HCl and HF, and carrying out product component analysis by chromatography, wherein the result is shown in table 1.
TABLE 1 preparation of R134a (CF) by different catalyst pairs 3 CH 2 F) Influence of (2)
Numbering Conversion of R133a (%) R134a Selectivity (%)
A 33.78 98.21
B 26.72 96.32
C 28.54 97.21
D 33.21 98.23
E 27.35 96.24
F 29.32 97.51
G 24.37 98.41
Test example 2
100mL of the catalysts prepared in examples 1 to 6 and comparative example 1 were charged in 316L,1 meter long DN25 stainless steel tubes, respectively. The catalyst was fixed in the middle, purged with nitrogen gas at 300 ℃ for 4 hours, and then HF and R124 (C) were introduced separately 2 HClF 4 ) The reaction is carried out, the molar ratio of HF to R124 is controlled to be 8:1, the reaction temperature is 350 ℃, certain reaction is carried out under the condition, the reaction product is washed by water and alkali to remove HCl and HF, and then product component analysis is carried out by chromatography, and the result is shown in table 2.
TABLE 2 preparation of R125 (CHF) with different catalyst pairs 2 CF 3 ) Influence of (2)
Figure BDA0002328367410000051
Figure BDA0002328367410000061
As can be seen from tables 1 and 2, the catalyst prepared by adding chromium nitrate to chromium chloride has higher activity, particularly, when the chromium nitrate content is higher, the fluorination catalyst has higher activity, while the catalyst prepared by not adding chromium nitrate in comparative example 1 has lower activity. According to thermodynamic calculation, the conversion rate of R134a prepared by catalyzing R133a by the fluorination catalyst is not more than 35% theoretically, and the conversion rate of the catalyst prepared by the method is similar to that of the catalyst, so that the catalyst has high activity.
The method uses the trifluoromethane as the fluorination reagent, can effectively avoid the problems that the hydrogen fluoride reacts violently as the common fluorination reagent, and the heat release is high, so that the catalyst is easy to sinter, and is beneficial to improving the stability of the catalyst.

Claims (8)

1. A preparation method of a solid fluorination catalyst comprises the following steps:
(1) Dissolving a mixture of chromium chloride and chromium nitrate and an auxiliary agent in deionized water to obtain a mixed salt solution; the mass ratio of the chromium nitrate to the chromium chloride is 0.1-12:1; the assistant is zinc nitrate;
(2) Adding the mixed salt solution obtained in the step (1) into a precipitant solution, controlling the pH value of the system to precipitate the salt solution, collecting and drying the precipitate, and roasting the precipitate in different atmospheres in sections to obtain a catalyst precursor; the step of sectional roasting is as follows: firstly, roasting the dried precipitate for 5-7h at 250-450 ℃ in nitrogen, and then roasting for 5-7h at 300-450 ℃ in mixed gas of air and nitrogen;
(3) Tabletting and forming the catalyst precursor obtained in the step (2), and then fluorinating the catalyst precursor by using trifluoromethane to obtain a fluorination catalyst: drying the catalyst precursor subjected to tabletting molding in a nitrogen atmosphere at 300 ℃ for 20-30h, introducing trifluoromethane, fluorinating at 300 ℃ for 80-120h, and naturally cooling to room temperature to obtain a fluorination catalyst; the flow rate of the trifluoromethane is 100-800mL/min.
2. The method for preparing the solid fluorination catalyst according to claim 1, wherein the mass ratio of the chromium nitrate to the chromium chloride in the step (1) is 3-10:1.
3. the method for preparing a solid fluorination catalyst according to claim 1, wherein the amount of the auxiliary added in step (1) is 10% of the total mass of the chromium chloride and the chromium nitrate.
4. The method for preparing a solid fluorination catalyst according to claim 1, wherein the precipitant solution in the step (2) is 5 to 15% by mass of aqueous ammonia.
5. The method for preparing a solid fluorination catalyst according to claim 1, wherein the pH of the system is controlled to 7 to 9 in the step (2).
6. The method for preparing a solid fluorination catalyst according to claim 1, wherein the drying temperature in the step (2) is 90 to 110 ℃ and the drying time is 5 to 8 hours.
7. The method for preparing a solid fluorination catalyst according to claim 1, wherein the volume ratio of air to nitrogen in the mixed gas in the step (2) is 2-10:1.
8. the method for preparing a solid fluorination catalyst according to claim 1, wherein the flow rate of trifluoromethane in the step (3) is 200 to 500mL/min; the fluorination time is 100h.
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