CN105936515B - A kind of preparation method for the catalyst precarsor and catalyst for synthesizing 1,1,1,2 HFC-134as - Google Patents
A kind of preparation method for the catalyst precarsor and catalyst for synthesizing 1,1,1,2 HFC-134as Download PDFInfo
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- C01G37/00—Compounds of chromium
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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
- 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
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Abstract
The invention discloses a kind of catalyst precarsor of 1,1,1,2 HFC-134a of synthesis, the catalyst precarsor is a kind of polynary houghite, and its chemical composition is [M2+ 1‑xM3+ x(OH)2]x+(An‑ x/n)·mH2O, wherein：M2+And M3+Divalence and trivalent metal ion, A are represented respectivelyn‑Anion is represented, x is M3+/(M2++M3+) mol ratio, n is 1 or 2, m are 0.3 0.7.The invention also discloses the method that catalyst is prepared using the catalyst precarsor.The present invention has the advantages that high activity, high stability and polymolecularity.
Description
Technical field
The present invention relates to catalyst field, particularly a kind of catalyst of synthesis HFA 134a (HFC-134a)
The preparation method of precursor and catalyst.
Background technology
At present, the synthesis of HFA 134a (HFC-134a) is typically with 1,1,1- trifluoro-2-chloroethane
(HCFC-133a) obtained with anhydrous hydrofluoric acid by exchange chloride for fluoride.Existing exchange chloride for fluoride catalyst substantially with
Al2O3Or AlF3Or MgF2It is carrier, the catalyst of load C r isoreactivity components Deng Al sources and Mg sources.At 300 DEG C -350 DEG C
Such catalyst is respectively 20% and 95% or so to R133a conversion ratio and R134a selectivity.
The current fluorination catalyst as disclosed in Chinese patent literature is large number of：
CN 1145275A disclose the catalysis that vapor phase method is synthesized HFC-134a reactions by trichloro ethylene with hydrogen fluoride reaction
Agent.It is specifically with containing SiO2γ-Al2O3The AlF for preparing porous high-specific surface area is reacted with anhydrous HF3Carrier, is then adopted again
With infusion process load C r3+, Co2+, Mg2+Etc. component, required catalyst is finally obtained.
CN 1099314A disclose a kind of by Cr, Al, In, the catalyst of Bi fluoride or oxyfluoride composition, and it is fitted
Freon substitute, such as HFC-134a are catalyzed and synthesized for vapor phase method.
CN 1091651C disclose a kind of catalyst for carrying out halogenated hydrocarbons fluorination with HF suitable for gas phase, specific catalysis
Agent is in carrier AlF3Or Al2O3Upper load C r, adds Mg, Ca, Sr, Ba, Ti, Zr a kind of auxiliary agent therein.
CN 101041132A disclose a kind of catalysts for gas phase fluorination, and gas is prepared by co-precipitation by Cr salt and Y salt
Phase fluorination catalysts precursor, then fired activation are obtained.
As can be seen here, based on Cr (III) compound, with Al2O3Or AlF3, MgF2For carrier, Co is added2+, Mg2+Deng auxiliary agent
Fluorination catalyst be known in the art, and be industrially widely used.However, such catalyst is in production and application
In there is following weak point：Such loaded catalyst causes active center distribution not by being also easy to produce avtive spot migration
, catalytic efficiency declines, and making the service life of catalyst is restricted.
The content of the invention
The purpose of the present invention is that there is provided a kind of high activity, high stability and height for weak point of the prior art
The catalyst precarsor and the preparation method of catalyst of the synthesis 1,1,1,2- HFC-134as of dispersiveness.
The present invention solve the technical scheme that uses of above-mentioned technical problem for：A kind of catalysis of synthesis 1,1,1,2- HFC-134as
Agent precursor, the catalyst precarsor is a kind of polynary houghite, and its chemical composition is [M2+ 1-xM3+ x(OH)2]x+(An- x/n)·
mH2O, wherein：M2+And M3+Divalence and trivalent metal ion, A are represented respectivelyn-Anion is represented, x is M3+/(M2++M3+) mole
Than n is 1 or 2 or 3, m are 0.3-0.7.
Further：
Described M2+For Mg2+、Mn2+、Co2+、Ni2+And Zn2+In one or more, described M3+For Cr3+Or Cr3+With
Al3+Or In3+At least one of mixture, described An-It is CO3 2-、OH-、NO3 -In one or more, described x is
0.1-0.5, preferably 0.16-0.33.
The present invention is with NaOH and Na2CO3Mixed solution be precipitating reagent, using double drop methods prepare laminated metal be combined hydrogen-oxygen
Compound catalyst precarsor, then catalyst precarsor is dried with nitrogen at ambient pressure, then anhydrous HF fluorination treatment is used, it is fluorinated
Catalyst.
The present invention also provides the method that catalyst is prepared using the catalyst precarsor, comprises the following steps：
(1) trivalent metal salt and divalent metal salt are configured to mixed solution I with deionized water by a certain percentage；By NaOH
With Na2CO3Mixed solution II is configured to deionized water by a certain percentage；
(2) mixed solution I and mixed solution II obtained step (1) is while be added drop-wise in deionized water, completion of dropping
30-60min is reacted at 60-100 DEG C afterwards, then crystallization 6-48h is carried out at 60-100 DEG C, washs and is filtered to neutrality, filter cake
In 60-90 DEG C of drying, cool down, crush, screening obtains catalyst precarsor；
(3) catalyst precarsor obtained by step (2) is led into nitrogen protective roast 2-8h, sintering temperature 200- at ambient pressure
500 DEG C, then lead to anhydrous HF activation process 6-48h, 200-500 DEG C of activation temperature obtains fluorination catalyst.
In mixed solution I described in step (1), the molal quantity of bivalent metal ion and the molal quantity of trivalent metal ion
Ratio is preferably 2-4:1.
In mixed solution I described in step (1), Cr3+Molal quantity and trivalent metal ion total mole number ratio it is preferred
For 0.1-1:1.
In mixed solution II described in step (1), NaOH and Na2CO3Mass ratio is preferably 4-10:1.
The ratio between the cumulative volume of mixed solution I and mixed solution II described in step (2) and the volume of deionized water are preferably
10-20:1。
Time for adding described in step (2) is preferably 0.5-1.5h.
The catalyst of the synthesis HFA 134a of the present invention includes activated centre and dispersible carrier, and its main points is：
Activated centre is Cr ions, from compound containing Cr, and dispersible carrier is two valencys or trivalent metal ion, with metal between them
Oxygen key is connected.
The catalyst of the present invention passes through simple regeneration, can recycle, further reduce three waste discharge, reduce into
This.Catalyst recovery process is：By the catalyst of recovery, nitrogen protective roast 2-8h, sintering temperature 200-500 are led at ambient pressure
DEG C, preferably 300-450 DEG C；Anhydrous HF activation process 6-48h is used again, and 200-500 DEG C of activation temperature is preferably 300-400 DEG C, natural
Room temperature is cooled to, regenerated catalyst is obtained.
Compared with prior art, the present invention has advantages below：
(1) catalyst active component is not easily runed off, and active component is more dispersed, and catalytic performance is higher；
(2) catalyst passes through simple regeneration, can recycle, further reduce three waste discharge, reduces cost, and
It is easy to industrialized production；
(3) compared with existing catalyst, higher conversion and selectivity are can guarantee that, and with high stability.
Embodiment
The present invention is described in further detail below by embodiment, but the present invention is not limited to these embodiments.
Embodiment 1
By Cr (NO3)3·9H2O 29.76g(0.125mol)、Al(NO3)3·9H2O 46.90g(0.125mol)、Mg
(NO3)2·6H2O 96.16g(0.375mol)、Zn(NO3)2·5H2O 111.56g (0.375mol) are configured to deionized water
300mL mixed solutions I, 300mL mixed solutions II are configured to deionized water by sodium hydroxide 40g and sodium carbonate 6.62g, standby
With.50mL deionized water is added into the 500ml four-hole bottles equipped with stirring, then by four-hole bottle heating water bath to 60 DEG C,
Stirring is opened, mixed solution I and mixed solution II are added drop-wise in four-hole bottle simultaneously, time for adding is 1h, and completion of dropping is follow-up
Continuous stirring 30min, in carrying out crystallization 24h at 65 DEG C, is washed with deionized to neutrality filtering, filter cake is cold in 80 DEG C of drying
But, crush, screening obtains catalyst precarsor.Catalyst precarsor is calcined 8h under normal pressure, the protection of logical nitrogen in 300 DEG C, then with nothing
Water HF handles 24h at 400 DEG C, obtains fluorination catalyst.Its reactivity and selectivity are shown in Tables 1 and 2.
Embodiment 2
By Cr (NO3)3·9H2O 42.84g(0.18mol)、Al(NO3)3·9H2O 67.52g(0.18mol)、Mg
(NO3)2·6H2O 92.30g(0.36mol)、Zn(NO3)2·5H2O 107.10g (0.36mol) are configured to deionized water
300mL mixed solutions I, 300mL mixed solutions II are configured to deionized water by sodium hydroxide 43.00g and sodium carbonate 9.39g,
It is standby.40mL deionized water is added into the 500ml four-hole bottles equipped with stirring, then by four-hole bottle heating water bath to 70
DEG C, stirring is opened, mixed solution I and mixed solution II are added drop-wise in four-hole bottle simultaneously, time for adding is 0.5h, completion of dropping
Continue to stir 40min afterwards, in carrying out crystallization 30h at 60 DEG C, filtering is washed with deionized to neutrality, filter cake is in 60 DEG C of bakings
It is dry, cool down, crush, screening obtains catalyst precarsor.Catalyst precarsor is calcined 3h in 200 DEG C under normal pressure, logical nitrogen protection, then
48h is handled at 200 DEG C with anhydrous HF, fluorination catalyst is obtained.Its reactivity and selectivity are shown in Tables 1 and 2.
Embodiment 3
By Cr (NO3)3·9H2O 28.56g(0.12mol)、Al(NO3)3·9H2O 90.02g(0.24mol)、Mg
(NO3)2·6H2O 92.30g(0.36mol)、Zn(NO3)2·5H2O 107.10g (0.36mol) are configured to deionized water
300mL mixed solutions I, 300mL mixed solutions II are configured to deionized water by sodium hydroxide 43.00g and sodium carbonate 9.39g,
It is standby.30mL deionized water is added into the 500ml four-hole bottles equipped with stirring, then by four-hole bottle heating water bath to 80
DEG C, stirring is opened, mixed solution I and mixed solution II are added drop-wise in four-hole bottle simultaneously, time for adding is 0.7h, completion of dropping
Continue to stir 50min afterwards, in carrying out crystallization 40h at 70 DEG C, filtering is washed with deionized to neutrality, filter cake is in 65 DEG C of bakings
It is dry, cool down, crush, screening obtains catalyst precarsor.Catalyst precarsor is calcined 4h in 250 DEG C under normal pressure, logical nitrogen protection, then
40h is handled at 300 DEG C with anhydrous HF, fluorination catalyst is obtained.Its reactivity and selectivity are shown in Tables 1 and 2.
Embodiment 4
By Cr (NO3)3·9H2O42.84g(0.18mol)、Mg(NO3)2·6H2O 92.30g(0.36mol)、Zn
(NO3)2·5H2O 107.10g (0.36mol) are configured to 300mL mixed solutions I with deionized water, by sodium hydroxide 35.00g and
Sodium carbonate 7.5g is configured to 300mL mixed solutions II with deionized water, standby.Added into the 500ml four-hole bottles equipped with stirring
60mL deionized water, then by four-hole bottle heating water bath to 90 DEG C, opens stirring, by mixed solution I and mixed solution II
It is added drop-wise to simultaneously in four-hole bottle, time for adding is to continue after 0.9h, completion of dropping to stir 55min, in carrying out crystallization at 80 DEG C
48h, is washed with deionized to neutrality filtering, and filter cake is cooled down in 70 DEG C of drying, crushed, and screening obtains catalyst precarsor.Urge
Agent precursor is calcined 6h under normal pressure, logical nitrogen protection in 400 DEG C, then handles 6h at 450 DEG C with anhydrous HF, obtains fluorination and urges
Agent.Its reactivity and selectivity are shown in Tables 1 and 2.
Embodiment 5
By Cr (NO3)3·9H2O 42.84g(0.18mol)、Al(NO3)3·9H2O 67.52g(0.18mol)、Mg
(NO3)2·6H2O 123.07g(0.48mol)、Zn(NO3)2·5H2O 71.40g (0.24mol) are configured to deionized water
300mL mixed solutions I, 300mL mixed solutions II are configured to deionized water by sodium hydroxide 43.00g and sodium carbonate 9.39g,
It is standby.35mL deionized water is added into the 500ml four-hole bottles equipped with stirring, then by four-hole bottle heating water bath to 100
DEG C, stirring is opened, mixed solution I and mixed solution II are added drop-wise in four-hole bottle simultaneously, time for adding is 1.2h, completion of dropping
Continue to stir 60min afterwards, in carrying out crystallization 6h at 90 DEG C, filtering be washed with deionized to neutrality, filter cake is dried in 85 DEG C,
Cooling, is crushed, and screening obtains catalyst precarsor.Catalyst precarsor is calcined 5h under normal pressure, logical nitrogen protection in 450 DEG C, then uses
Anhydrous HF handles 12h at 500 DEG C, obtains fluorination catalyst.Its reactivity and selectivity are shown in Tables 1 and 2.
Embodiment 6
By Cr (NO3)3·9H2O 42.84g(0.18mol)、Al(NO3)3·9H2O 56.27g(0.15mol)、In
(NO3)3·H2O9.50g(0.03mol)、Mg(NO3)2·6H2O 92.30g(0.36mol)、Zn(NO3)2·5H2O 107.10g
(0.36mol) is configured to 300mL mixed solutions I with deionized water, by sodium hydroxide 43.00g and sodium carbonate 9.39g deionizations
Water is configured to 300mL mixed solutions II, standby.45mL deionized water is added into the 500ml four-hole bottles equipped with stirring, then
By four-hole bottle heating water bath to 85 DEG C, stirring is opened, mixed solution I and mixed solution II are added drop-wise in four-hole bottle simultaneously,
Time for adding is to continue after 1.5h, completion of dropping to stir 45min, in carrying out crystallization 12h at 100 DEG C, be washed with deionized to
Filtered after neutrality, filter cake is cooled down in 90 DEG C of drying, is crushed, and screening obtains catalyst precarsor.Catalyst precarsor is in normal pressure, logical nitrogen
2h is calcined in 500 DEG C under gas shielded, then 30h is handled at 350 DEG C with anhydrous HF, fluorination catalyst is obtained.Its reactivity and
Selectivity is shown in Tables 1 and 2.
Activity and HFC134a selectivity (HF of the catalyst that the embodiment 1-6 of table 1 is prepared to HCFC133a:
HCFCl33a=8:1, air speed：2500h-1, reaction product by washing alkali cleaning after, detected with GC)
Activity to HCFC133a and HFC134a choosing after the long-lasting catalytic use that the embodiment 1-6 of table 2 is prepared
Selecting property (HF:HCFCl33a=8:1, air speed：2500h-1, reaction product by washing alkali cleaning after, detected with GC).
Claims (7)
1. a kind of catalyst precarsor for synthesizing HFA 134a, it is characterised in that the catalyst precarsor is a kind of polynary
Houghite, its chemical composition is [M2+ 1-xM3+ x(OH)2]x+(An- x/n)·mH2O, wherein：M2+And M3+Divalence and three are represented respectively
Valence metal ion, An-Anion is represented, x is M3+/(M2++M3+) mol ratio, n be 1 or 2 or 3, m be 0.3-0.7, described M2 +For Mg2+、Mn2+、Co2+、Ni2+And Zn2+In one or more, described M3+For Cr3+Or Cr3+With Al3+Mixture or Cr3+
With Al3+And In3+Mixture, described An-It is CO3 2-、OH-、NO3 -In one or more, described x is 0.1-0.5.
2. the method that the catalyst precarsor described in usage right requirement 1 prepares catalyst, it is characterised in that comprise the following steps：
(1) trivalent metal salt and divalent metal salt are configured to mixed solution I with deionized water by a certain percentage；By NaOH with
Na2CO3Mixed solution II is configured to deionized water by a certain percentage；
(2) mixed solution I and mixed solution II that obtain step (1) while be added drop-wise in deionized water, after completion of dropping
30-60min is reacted at 60-100 DEG C, then filtering after crystallization 6-48h, washing to neutrality is carried out at 60-100 DEG C, filter cake is in 60-
90 DEG C of drying, are cooled down, and are crushed, and screening obtains catalyst precarsor；
(3) catalyst precarsor obtained by step (2) is led into nitrogen protective roast 2-8h, sintering temperature 200-500 at ambient pressure
DEG C, then lead to anhydrous HF activation process 6-48h, 200-500 DEG C of activation temperature obtains fluorination catalyst.
3. preparation method according to claim 2, it is characterised in that in the mixed solution I described in step (1), divalent metal
The ratio of the molal quantity of ion and the molal quantity of trivalent metal ion is 2-4:1.
4. preparation method according to claim 2, it is characterised in that in the mixed solution I described in step (1), Cr3+Rub
The ratio of the total mole number of that number and trivalent metal ion is 0.1-1:1.
5. preparation method according to claim 2, it is characterised in that in the mixed solution II described in step (1), NaOH with
Na2CO3Mass ratio is 4-10:1.
6. preparation method according to claim 2, it is characterised in that mixed solution I and mixed solution described in step (2)
The ratio between II cumulative volume and the volume of deionized water are 10-20:1.
7. preparation method according to claim 2, it is characterised in that the time for adding described in step (2) is 0.5-1.5h.
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| CN106565412A (en) * | 2016-11-08 | 2017-04-19 | 衢州学院 | Device and method for preparing 1,1,1,2-tetrafluoroethane |
| CN107376952B (en) * | 2017-06-09 | 2020-05-05 | 浙江三美化工股份有限公司 | Preparation method of tetrafluoroethane catalyst |
| CN112642449A (en) * | 2020-12-21 | 2021-04-13 | 江苏三美化工有限公司 | Catalyst for gas phase fluorination of 1,1,1, 2-tetrafluoroethane and preparation method thereof |
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Effective date of registration: 20180712 Address after: 226407 Yang Kou Town Chemical Industrial Park, Rudong, Nantong, Jiangsu Patentee after: JIANGSU SANMEI CHEMICALS CO., LTD. Address before: 324000 North China Road No. 78, Quzhou, Quzhou, Zhejiang Patentee before: Quzhou University |
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