CN107930656A - 2 chlorine, 3,3,3 trifluoro propene prepares 2,3,3,3 tetrafluoropropene catalyst - Google Patents
2 chlorine, 3,3,3 trifluoro propene prepares 2,3,3,3 tetrafluoropropene catalyst Download PDFInfo
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- CN107930656A CN107930656A CN201711146997.1A CN201711146997A CN107930656A CN 107930656 A CN107930656 A CN 107930656A CN 201711146997 A CN201711146997 A CN 201711146997A CN 107930656 A CN107930656 A CN 107930656A
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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
- 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
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
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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
- 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
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- 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
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
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- 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
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Abstract
The invention discloses a kind of 3,3,3 trifluoro propene of 2 chlorine to prepare 2,3,3,3 tetrafluoropropene catalyst, and catalyst composition is MxOy‑Cr2O3/AlF3, wherein MxOyFor MgO, Co3O4、ZnO、SnO2Or Sb2O3In one kind.The preparation method of catalyst comprises the following steps：(1) hydrofluoric acid is instilled in the polyhydric alcohol solutions of inorganic aluminate or the polyalcohol slurries of boehmite, obtains lyosol；(2) by lyosol, aging obtains solid gel at 60~90 DEG C；(3) solid gel is dried to obtain to the AlF of high-specific surface area, meso-hole structure at 100~160 DEG C3Carrier；(4) by the method for substep or co-impregnation, active component Cr and auxiliary agent M are supported on carrier, Cr and AlF3Molar ratio be 0.05~0.3:1, M and AlF3Molar ratio be 0.01~0.1:1, through drying, roasting, required catalyst is obtained, auxiliary agent M is one kind in Mg, Co, Zn, Sn or Sb.Catalyst activity in the present invention is high, and stability is good, is not required to be passed through oxidizing gas in reaction process, has industrial applications value.
Description
Technical field
The present invention relates to a kind of catalyst, and in particular to one kind is used for 2- chloro-3,3,3 ,-trifluoropropenes and prepares 2,3,3,3-
The catalyst of tetrafluoropropene.
Background technology
2,3,3,3- tetrafluoropropenes (HFO-1234yf) ozone-depleting value (ODP) of diving is zero, global warming potential (GWP)
It is low, it is new generation of green environmental protection refrigerant.HFO-1234yf or synthesizing high-stability, the polymerization list of high elastic rubber plastics
Body, is widely used in the fields such as fire-fighting, aerospace.With 2- chloro-3,3,3 ,-trifluoropropenes (HCFO-1233xf) for raw material, warp
It is an economically viable route that gas phase catalytic fluorination, which prepares HFO-1234yf,.
Industrial＆Engineering Chemistry Research, 2013,52,3295-3299 report Cr2O3
The catalyst of HFO-1234yf is prepared as HCFO-1233xf, in 320 DEG C of reactions, HCFO-1233xf conversion ratios are 63.3%,
HFO-1234yf is selectively 58.2%, poor catalyst stability, easy in inactivation, and after reacting 30h, activity is more than drop by half.
Applied Catalysis B:Environmental, 2015,165,200-208 report the chromium oxide of fluorination
(F-Cr2O3) catalyst of HFO-1234yf is prepared as HCFO-1233xf, in the presence of the air, in 350 DEG C of reactions, HCFO-
1233xf conversion ratios are that 69%, HFO-1234yf selectivity is 59%, and reaction temperature is higher.
Patent CN102989489A reports Cr1(Y、Z)0.005~0.5O0.1~1.0F1.0~3.0Prepared as HCFO-1233xf
The catalyst of HFO-1234yf, wherein Y are selected from one or both of Al, Zn or Mg combination of the above, and Z is with oxygen storing discharging
The rare earth element of function, in 400 DEG C of reactions, is not passed through O2When, HCFO-1233xf conversion ratios only have 10.3%, catalyst activity
It is low；It is passed through O2When, HCFO-1233xf conversion ratios are that 68.4%, HFO-1234yf selectivity is 87.3%.
Patent US8207383B reports Cr-Ni/AlF3The catalyst of HFO-1234yf is prepared as HCFO-1233xf,
In 352 DEG C of reactions, HCFO-1233xf conversion ratios only have 10.3%, and catalyst activity is low.
At present HCFO-1233xf prepare HFO-1234yf catalyst exist activity it is low, stability is poor, reaction temperature is high,
The problem of needing to be passed through oxidizing gas, increase later stage separation costs in reaction process.
The content of the invention
The present invention is insufficient existing for catalyst in the prior art to solve, there is provided a kind of activity is high, and reaction temperature is low, instead
It is not required to be passed through oxidizing gas during answering, the HCFO-1233xf of service life length prepares the catalyst of HFO-1234yf.
In order to achieve the object of the present invention, a kind of activity height is obtained, reaction temperature is low, is not required to be passed through oxidation in reaction process
Property gas, service life length catalyst, it is contemplated that using with high-specific surface area, the AlF of meso-hole structure3As active carrier,
Cr is as active component, and one kind in Mg, Co, Zn, Sn or Sb is as auxiliary agent, by active component and the synergistic effect of auxiliary agent,
Catalyst needed for acquisition.
The catalyst composition that HCFO-1233xf of the present invention prepares HFO-1234yf is MxOy-Cr2O3/AlF3, wherein
MxOyFor MgO, Co3O4、ZnO、SnO2Or Sb2O3In one kind；The preparation method of the catalyst comprises the following steps：
(1) under stirring, hydrofluoric acid is instilled in the polyhydric alcohol solutions of inorganic aluminate or the polyalcohol slurries of boehmite,
Fluorination treatment is carried out, hydrofluoric acid is 3~6 with inorganic aluminate or boehmite molar ratio:1, continue to stir 6h after being added dropwise
More than, obtain lyosol；
The inorganic aluminate is one kind in aluminum nitrate, aluminium chloride or aluminum sulfate；
The polyalcohol is one kind in ethylene glycol, 1,2- propane diols or 1,3- propane diols；
(2) lyosol is stood into more than aging 24h at 60~90 DEG C, obtains solid gel；
(3) solid gel is obtained into the AlF of high-specific surface area, meso-hole structure in 100~160 DEG C of dry more than 24h3It is living
Property carrier；
(4) by the method for substep or co-impregnation, active component Cr and auxiliary agent M are supported on AlF3On carrier, after dry
Roast at high temperature, obtain required catalyst, the auxiliary agent M is one kind in Mg, Co, Zn, Sn or Sb, active component Cr and load
Body AlF3Molar ratio be 0.05~0.3:1, auxiliary agent M and carrier AlF3Molar ratio be 0.01~0.1:1；
The method of the step impregnation is that the aqueous solution of the soluble-salt of chromium is impregnated AlF3Carrier, it is dry in 90~120 DEG C
It is dry to obtain solid, the aqueous solution of the soluble-salt of auxiliary agent M is impregnated into above-mentioned solid, in 90~120 DEG C of dryings, finally 250~
Roasted at 350 DEG C, obtain required catalyst, the soluble-salt of the chromium is Cr (NO3)3Or CrCl3In one kind, the auxiliary agent M
Soluble-salt be Mg (NO3)2、Co(NO3)2、Zn(NO3)2、MgCl2、CoCl2、ZnCl2、SnCl4、SbCl3Or SbF3In one
Kind；
The method of the co-impregnation is that will impregnate AlF containing the mixing salt solution of chromium and auxiliary agent M3Carrier, in 90~120 DEG C
It is dry, finally roasted at 250~350 DEG C, obtain required catalyst, the mixing salt solution of chromium and the auxiliary agent M is by Cr (NO3)3
Or CrCl3In one kind and Mg (NO3)2、Co(NO3)2、Zn(NO3)2、MgCl2、CoCl2、ZnCl2、SnCl4、SbCl3Or SbF3In
A kind of prepare obtain.
A kind of preferable HCFO-1233xf prepares the catalyst of HFO-1234yf, MxOyPreferably ZnO or Sb2O3。
Beneficial effects of the present invention：Compared with prior art, the present invention has the following advantages：
(1) existing catalyst reaction temperatures are high, and activity is low, needs to be passed through oxidizing gas in reaction process to improve activity,
With Cr1(Y、Z)0.005~0.5O0.1~1.0F1.0~3.0For catalyst, in 400 DEG C of reactions, O is not passed through2When, HCFO-1233xf conversion ratios
Only 10.3%, catalyst activity is low；It is passed through O2When, HCFO-1233xf conversion ratios can bring up to 68.4%, be catalyzed in the present invention
Agent has high activity, and is not required to be passed through oxidizing gas, during 320 DEG C of reactions, HCFO-1233xf conversion ratios up to 65% with
On, reach as high as 80%.
(2) existing poor catalyst stability, with Cr2O3For catalyst, reacted in 320 DEG C, HCFO-1233xf initial conversions
Rate is 63.3%, and after reacting 30h, activity is more than drop by half, and catalyst stability is good in the present invention, and long lifespan, can stablize
Run 360h.
Embodiment
The specific embodiment of the present invention is given below, but does not limit the scope of the invention.
The evaluation of catalyst performance：60mL catalyst is measured to be fitted into the fixed-bed tube reactor that caliber is Φ 38mm,
260 DEG C are warming up to, dry at least 2h, is passed through hydrogen fluoride gas and is fluorinated 2~4h, then heat to 350 DEG C, continue 2~4h of fluorination,
320 DEG C are cooled to, it is 9, time of contact 10s to be passed through HCFO-1233xf, HF and HCFO-1233xf molar ratio, runs 24h, instead
Product is answered to be analyzed after washing, alkali cleaning absorb HF by gas-chromatography, analysis method is area normalization method, obtains raw material and turns
The selective data of rate and HFO-1234yf.
Embodiment 1
Under stirring, the hydrofluoric acid that 75g mass fractions are 40% is instilled to the second two for the aluminum nitrate that 500mL concentration is 1mol/L
In alcoholic solution, fluorination treatment is carried out, continues to stir more than 6h after being added dropwise, obtains lyosol；By lyosol at 70 DEG C
More than aging 24h is stood, obtains solid gel；By solid gel in 120 DEG C of dry more than 24h, 40.0g high-ratio surfaces are obtained
Product, the aluminum fluoride active carrier of meso-hole structure；2.1g magnesium nitrates and 11.3g chromic nitrates are dissolved in 30mL deionized waters and prepare nitre
The mixed solution of sour magnesium and chromic nitrate, then mixed solution impregnate above-mentioned fluorination alumina supporter, 100 DEG C of dryings in baking oven, in horse
Not 300 DEG C of roastings of stove, are made catalyst.By evaluation, HCFO-1233xf conversion ratios are 70.2%, HFO-1234yf selectivity
For 82.5%.
Embodiment 2
Under stirring, the hydrofluoric acid that 100g mass fractions are 40% is instilled the 1 of the aluminium chloride that 500mL concentration is 1mol/L,
In 2- propylene glycol solutions, fluorination treatment is carried out, continues to stir more than 6h after being added dropwise, obtains lyosol；By lyosol
More than aging 24h is stood at 80 DEG C, obtains solid gel；By solid gel in 140 DEG C of dry more than 24h, 41.2g high ratios are obtained
The aluminum fluoride active carrier of surface area, meso-hole structure；4.5g cobalt chlorides and 26.1g chromium chlorides are dissolved in 30mL deionized waters and matched somebody with somebody
The mixed solution of cobalt chloride and chromium chloride processed, then mixed solution impregnate above-mentioned fluorination alumina supporter, 110 DEG C of dryings in baking oven,
In 320 DEG C of roastings of Muffle furnace, catalyst is made.By evaluation, HCFO-1233xf conversion ratios select for 65.8%, HFO-1234yf
Selecting property is 85.1%.
Embodiment 3
Under stirring, the hydrofluoric acid that 125g mass fractions are 40% is instilled into the aluminum sulfate that 1000mL concentration is 0.5mol/L
In 1,3-PD solution, fluorination treatment is carried out, continues to stir more than 6h after being added dropwise, obtains lyosol；Liquid is molten
Glue stands more than aging 24h at 90 DEG C, obtains solid gel；By solid gel in 160 DEG C of dry more than 24h, 41.8g high is obtained
The aluminum fluoride active carrier of specific surface area, meso-hole structure；It is molten that 35.5g chromic nitrates are dissolved in preparation chromic nitrate in 30mL deionized waters
Liquid, impregnates above-mentioned fluorination alumina supporter, and 72.4g solids are dried to obtain for 120 DEG C in baking oven, by 6.8g zinc chloride be dissolved in 30mL go from
Liquor zinci chloridi is prepared in sub- water, then impregnates above-mentioned solid, 120 DEG C of dryings in baking oven, in 350 DEG C of roastings of Muffle furnace, system
Into catalyst.By evaluation, HCFO-1233xf conversion ratios are that 77.5%, HFO-1234yf selectivity is 82.8%.
Embodiment 4
Under stirring, the hydrofluoric acid instillation 250mL that 125g mass fractions are 40% is contained to the boehmite of 0.5mol
In ethylene glycol slurries, fluorination treatment is carried out, continues to stir more than 6h after being added dropwise, obtains lyosol；Lyosol is existed
60 DEG C of standing more than aging 24h, obtain solid gel；By solid gel in 100 DEG C of dry more than 24h, obtain 41.5g high and compare table
The aluminum fluoride active carrier of area, meso-hole structure；1.3g stannic chlorides and 3.9g chromium chlorides are dissolved in 30mL deionized waters and prepared
The mixed solution of stannic chloride and chromium chloride, then mixed solution impregnate above-mentioned fluorination alumina supporter, 90 DEG C of dryings in baking oven, in horse
Not 250 DEG C of roastings of stove, are made catalyst.By evaluation, HCFO-1233xf conversion ratios are 67.0%, HFO-1234yf selectivity
For 72.9%.
Embodiment 5
Under stirring, the hydrofluoric acid that 60g mass fractions are 60% is instilled the 1 of the boehmite that 500mL contains 0.5mol,
In ammediol slurries, fluorination treatment is carried out, continues to stir more than 6h after being added dropwise, obtains lyosol；By lyosol
More than aging 24h is stood at 80 DEG C, obtains solid gel；By solid gel in 140 DEG C of dry more than 24h, 39.6g high ratios are obtained
The aluminum fluoride active carrier of surface area, meso-hole structure；It is molten that 16.8g chromic nitrates are dissolved in preparation chromic nitrate in 30mL deionized waters
Liquid, impregnates above-mentioned fluorination alumina supporter, and 56.4g solids are dried to obtain for 110 DEG C in baking oven, and 6.7g antimony trifluorides are dissolved in 30mL
Antimony trifluoride solution is prepared in ionized water, then impregnates above-mentioned solid, 110 DEG C of dryings in baking oven, in 310 DEG C of roastings of Muffle furnace
Burn, catalyst is made.By evaluation, HCFO-1233xf conversion ratios are that 75.3%, HFO-1234yf selectivity is 78.4%.
Embodiment 6
Under stirring, the hydrofluoric acid that 40g mass fractions are 75% is instilled into 500mL and contains the 1,2- of 0.5mol boehmites
In propane diols slurries, fluorination treatment is carried out, continues to stir more than 6h after being added dropwise, obtains lyosol；Lyosol is existed
70 DEG C of standing more than aging 24h, obtain solid gel；By solid gel in 130 DEG C of dry more than 24h, obtain 38.8g high and compare table
The aluminum fluoride active carrier of area, meso-hole structure；3.8g zinc chloride and 19.8g chromic nitrates are dissolved in 30mL deionized waters and prepared
The mixed solution of zinc chloride and chromic nitrate, then mixed solution impregnate above-mentioned fluorination alumina supporter, 110 DEG C of dryings in baking oven,
300 DEG C of roastings of Muffle furnace, are made catalyst.By evaluation, HCFO-1233xf conversion ratios select for 80.6%, HFO-1234yf
Property is 84.7%.
Embodiment 7
Under stirring, the hydrofluoric acid that 100g mass fractions are 40% is instilled the 1 of the aluminum nitrate that 250mL concentration is 2mol/L,
In 2- propylene glycol solutions, fluorination treatment is carried out, continues to stir more than 6h after being added dropwise, obtains lyosol；By lyosol
More than aging 24h is stood at 60 DEG C, obtains solid gel；By solid gel in 100 DEG C of dry more than 24h, 39.3g high ratios are obtained
The aluminum fluoride active carrier of surface area, meso-hole structure；0.9g zinc nitrates and 7.4g chromium chlorides are dissolved in 30mL deionized waters and matched somebody with somebody
The mixed solution of zinc nitrate and chromium chloride processed, then mixed solution impregnate above-mentioned fluorination alumina supporter, 90 DEG C of dryings in baking oven,
250 DEG C of roastings of Muffle furnace, are made catalyst.By evaluation, HCFO-1233xf conversion ratios select for 73.8%, HFO-1234yf
Property is 79.5%.
The HCFO-1233xf of the present invention prepares HFO-1234yf and is tested with catalyst life
Life test, loaded catalyst 60mL are carried out to catalyst prepared by embodiment 3, reaction temperature is 320 DEG C, HF
It is 9, time of contact 10s with HCFO-1233xf molar ratios, reacts continuous service 360h, reaction product is absorbed through washing, alkali cleaning
Analyzed after HF by gas-chromatography, evaluation result is shown in Table 1.
1 life test of table
| Reaction time | HCFO-1233xf conversion ratios, % | HFO-1234yf selectivity, % |
| 24h | 77.5 | 82.8 |
| 120h | 75.8 | 83.4 |
| 240h | 74.6 | 82.5 |
| 360h | 73.4 | 81.8 |
Claims (2)
1. a kind of 2- chloro-3,3,3 ,-trifluoropropenes prepare 2,3,3,3- tetrafluoropropene catalyst, it is characterised in that the catalysis
Agent composition is MxOy-Cr2O3/AlF3, wherein MxOyFor MgO, Co3O4、ZnO、SnO2Or Sb2O3In one kind；The catalyst
Preparation method comprises the following steps：
(1) under stirring, hydrofluoric acid is instilled in the polyhydric alcohol solutions of inorganic aluminate or the polyalcohol slurries of boehmite, carried out
Fluorination treatment, hydrofluoric acid are 3~6 with inorganic aluminate or boehmite molar ratio:1, continue to stir more than 6h after being added dropwise,
Obtain lyosol；
The inorganic aluminate is one kind in aluminum nitrate, aluminium chloride or aluminum sulfate；
The polyalcohol is one kind in ethylene glycol, 1,2- propane diols or 1,3- propane diols；
(2) lyosol is stood into more than aging 24h at 60~90 DEG C, obtains solid gel；
(3) solid gel is obtained into the AlF of high-specific surface area, meso-hole structure in 100~160 DEG C of dry more than 24h3Activity carries
Body；
(4) by the method for substep or co-impregnation, active component Cr and auxiliary agent M are supported on AlF3On carrier, in high temperature after drying
Lower roasting, obtains required catalyst, and the auxiliary agent M is one kind in Mg, Co, Zn, Sn or Sb, active component Cr and carrier AlF3
Molar ratio be 0.05~0.3:1, auxiliary agent M and carrier AlF3Molar ratio be 0.01~0.1:1；
The method of the step impregnation is that the aqueous solution of the soluble-salt of chromium is impregnated AlF3Carrier, is dried to obtain in 90~120 DEG C
Solid, impregnates above-mentioned solid, in 90~120 DEG C of dryings, finally at 250~350 DEG C by the aqueous solution of the soluble-salt of auxiliary agent M
Roasting, obtains required catalyst, the soluble-salt of the chromium is Cr (NO3)3Or CrCl3In one kind, the auxiliary agent M's is solvable
Property salt is Mg (NO3)2、Co(NO3)2、Zn(NO3)2、MgCl2、CoCl2、ZnCl2、SnCl4、SbCl3Or SbF3In one kind；
The method of the co-impregnation is that will impregnate AlF containing the mixing salt solution of chromium and auxiliary agent M3Carrier, in 90~120 DEG C of dryings,
Finally roasted at 250~350 DEG C, obtain required catalyst, the mixing salt solution of chromium and the auxiliary agent M is by Cr (NO3)3Or
CrCl3In one kind and Mg (NO3)2、Co(NO3)2、Zn(NO3)2、MgCl2、CoCl2、ZnCl2、SnCl4、SbCl3Or SbF3In
One kind is prepared and obtained.
2. 2- chloro-3,3,3 ,-trifluoropropenes according to claim 1 prepare 2,3,3,3- tetrafluoropropene catalyst, it is special
Sign is, MxOyFor ZnO or Sb2O3。
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| CN114644546A (en) * | 2020-12-17 | 2022-06-21 | 陕西中蓝化工科技新材料有限公司 | Preparation method of fluoroolefin |
| CN117983233A (en) * | 2024-04-03 | 2024-05-07 | 淄博飞源化工有限公司 | Catalyst for synthesizing 2, 3-tetrafluoropropene and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114644546A (en) * | 2020-12-17 | 2022-06-21 | 陕西中蓝化工科技新材料有限公司 | Preparation method of fluoroolefin |
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| CN112794788B (en) * | 2021-04-08 | 2021-07-09 | 泉州宇极新材料科技有限公司 | Method for synthesizing fluoroisobutylene by using hexafluoropropylene as starting material |
| CN117983233A (en) * | 2024-04-03 | 2024-05-07 | 淄博飞源化工有限公司 | Catalyst for synthesizing 2, 3-tetrafluoropropene and preparation method thereof |
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