CN105936515A - Synthesis method of 1,1,1,2- tetrafluoroethane catalyst precursor and catalyst - Google Patents
Synthesis method of 1,1,1,2- tetrafluoroethane catalyst precursor and catalyst Download PDFInfo
- Publication number
- CN105936515A CN105936515A CN201511021892.4A CN201511021892A CN105936515A CN 105936515 A CN105936515 A CN 105936515A CN 201511021892 A CN201511021892 A CN 201511021892A CN 105936515 A CN105936515 A CN 105936515A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- mixed solution
- deionized water
- catalyst precarsor
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/006—Compounds containing, besides chromium, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of 1,1,1,2-tetrafluoroethane catalyst precursor. The catalyst precursor is a multicomponent hydrotalcite with chemical composition of [M2+1-xM3+x (OH)2]x+(An-x /n).mH2O, wherein M2+ and M3 + respectively represent divalent and trivalent metal ions, An-x represents anion, x represents the molar ratio of M3+/ (M2++M3+), n is 1 or 2, and m is 0.3-0.7. The invention also discloses a method for preparing a catalyst by using the catalyst precursor. The invention has the advantages of high activity, high stability and high dispersion.
Description
Technical field
The present invention relates to catalyst field, before the catalyst of particularly a kind of synthesis HFA 134a (HFC-134a)
Body and the preparation method of catalyst.
Background technology
At present, the synthesis of HFA 134a (HFC-134a) is typically with 1,1,1-trifluoro-2-chloroethane (HCFC-133a)
Obtained by exchange chloride for fluoride with anhydrous hydrofluoric acid.Existing exchange chloride for fluoride catalyst is substantially with Al2O3Or
AlF3Or MgF2It is carrier in Al source and Mg source, the catalyst of load C r isoreactivity component.At 300 DEG C-350
At DEG C, such catalyst is respectively 20% and about 95% to the conversion ratio of R133a and the selectivity of R134a.
The most large number of by fluorination catalyst disclosed in Chinese patent literature:
CN 1145275A discloses the catalysis that vapor phase method is reacted with hydrogen fluoride reaction synthesis HFC-134a by trichloro ethylene
Agent.It is specifically with containing SiO2γ-Al2O3With the AlF that anhydrous HF reacts preparation porous high-specific surface area3Carrier, so
After use infusion process load C r again3+, Co2+, Mg2+Etc. component, finally obtain required catalyst.
CN 1099314A discloses a kind of by Cr, the fluoride of Al, In, Bi or the catalyst of oxyfluoride composition,
It is applicable to vapor phase method and catalyzes and synthesizes freon succedaneum, such as HFC-134a.
CN 1091651C discloses a kind of catalyst carrying out halogenated hydrocarbons fluorination be applicable to gas phase with HF, is specifically catalyzed
Agent is at carrier AlF3Or Al2O3Upper load C r, adds Mg, Ca, Sr, Ba, Ti, Zr a kind of auxiliary agent therein.
CN 101041132A discloses a kind of catalysts for gas phase fluorination, Cr salt and Y salt are prepared by co-precipitation
Catalysts for gas phase fluorination precursor, more fired activation acquisition.
As can be seen here, based on Cr (III) compound, with Al2O3Or AlF3, MgF2For carrier, add Co2+, Mg2+
It is to it known in the art, and be industrially widely used Deng the fluorination catalyst of auxiliary agent.But, such catalyst
In production and application, there is following weak point: such loaded catalyst is migrated by being easily generated avtive spot, cause living
Property central distribution uneven, catalytic efficiency declines, and the service life making catalyst is restricted.
Summary of the invention
It is an object of the invention to for weak point of the prior art, it is provided that a kind of high activity, high stability and high score
Dissipate catalyst precarsor and the preparation method of catalyst of the synthesis 1,1,1,2-tetrafluoroethane of property.
The present invention solves the technical scheme of above-mentioned technical problem employing: a kind of catalyst synthesizing 1,1,1,2-tetrafluoroethane
Precursor, described 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+Represent bivalence and trivalent metal ion, A respectivelyn-
Representing anion, x is M3+/(M2++M3+) mol ratio, n is 1 or 2 or 3, and m is 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+In the mixture of at least one, described An-It is CO3 2-、OH-、NO3 -In one
Or multiple, described x is 0.1-0.5, preferably 0.16-0.33.
The present invention is with NaOH and Na2CO3Mixed solution be precipitant, use double dripping method to prepare laminated metal and be combined hydrogen
Oxide catalyst precursor, then catalyst precarsor is dried with under nitrogen at ambient pressure, then use anhydrous HF fluorination treatment,
Obtain fluorination catalyst.
The present invention also provides for the method using this catalyst precarsor to prepare catalyst, 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；Will
NaOH and Na2CO3It is configured to mixed solution II by a certain percentage with deionized water；
(2) mixed solution I and the mixed solution II step (1) obtained is simultaneously added dropwise in deionized water, drips
At 60-100 DEG C, react 30-60min after Biing, then at 60-100 DEG C, carry out crystallization 6-48h, wash and filter to neutrality,
Filter cake, in 60-90 DEG C of drying, cooling, crushes, and screening obtains catalyst precarsor；
(3) catalyst precarsor obtained by step (2) is led to nitrogen protective roast 2-8h, sintering temperature at ambient pressure
200-500 DEG C, then lead to anhydrous HF activation processing 6-48h, activation temperature 200-500 DEG C, obtain 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 be preferably 2-4:1.
In mixed solution I described in step (1), Cr3+Molal quantity preferred with the ratio of the total mole number of trivalent metal ion
For 0.1-1:1.
In mixed solution II described in step (1), NaOH and Na2CO3Mass ratio is preferably 4-10:1.
Mixed solution I described in step (2) and the cumulative volume of mixed solution II are preferably with the ratio of the volume of deionized water
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 active center and dispersible carrier, and it is characterized by: live
Property center is Cr ion, derives from containing Cr compound, and dispersible carrier is two valencys or trivalent metal ion, between them with
Metal oxygen key is connected.
The catalyst of the present invention, through simple regeneration, can recycle, further reduce three waste discharge, reduce into
This.Catalyst recovery process is: the catalyst that will reclaim, and leads to nitrogen protective roast 2-8h, sintering temperature at ambient pressure
200-500 DEG C, preferably 300-450 DEG C；Again by anhydrous HF activation processing 6-48h, activation temperature 200-500 DEG C, preferably
300-400 DEG C, naturally cool to room temperature, obtain regenerated catalyst.
Compared with prior art, the invention have the advantages that
(1) catalyst active component not easily runs off, and active component ratio is relatively decentralized, and catalytic performance is higher；
(2) catalyst is through simple regeneration, can recycle, further reduce three waste discharge, reduce cost,
And it is prone to industrialized production；
(3) compared with existing catalyst, can guarantee that higher conversion and selectivity, and there is high stability.
Detailed description of the invention
Below by embodiment, the present invention is described in further detail, 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) joins with deionized water
Make 300mL mixed solution I, sodium hydroxide 40g and sodium carbonate 6.62g deionized water are configured to 300mL and mix
Close solution II, standby.The deionized water of 50mL is added, then by four-hole bottle in the 500ml four-hole bottle equipped with stirring
With heating in water bath to 60 DEG C, open stirring, mixed solution I and mixed solution II are simultaneously added dropwise in four-hole bottle, dropping
Time is 1h, drips complete follow-up continuous stirring 30min, carries out crystallization 24h at 65 DEG C, be washed with deionized in
Filtering after property, filter cake is in 80 DEG C of drying, cooling, and broken, screening obtains catalyst precarsor.Catalyst precarsor normal pressure,
In 300 DEG C of roasting 8h under logical nitrogen protection, then at 400 DEG C, process 24h by anhydrous HF, obtain 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) prepares with deionized water
Become 300mL mixed solution I, sodium hydroxide 43.00g and sodium carbonate 9.39g deionized water are configured to 300mL and mix
Close solution II, standby.The deionized water of 40mL is added, then by four-hole bottle in the 500ml four-hole bottle equipped with stirring
With heating in water bath to 70 DEG C, open stirring, mixed solution I and mixed solution II are simultaneously added dropwise in four-hole bottle, dropping
Time is 0.5h, drips complete follow-up continuous stirring 40min, carries out crystallization 30h at 60 DEG C, be washed with deionized to
Filtering after neutrality, filter cake is in 60 DEG C of drying, cooling, and broken, screening obtains catalyst precarsor.Catalyst precarsor normal pressure,
In 200 DEG C of roasting 3h under logical nitrogen protection, then at 200 DEG C, process 48h by anhydrous HF, obtain fluorination catalyst.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) prepares with deionized water
Become 300mL mixed solution I, sodium hydroxide 43.00g and sodium carbonate 9.39g deionized water are configured to 300mL and mix
Close solution II, standby.The deionized water of 30mL is added, then by four-hole bottle in the 500ml four-hole bottle equipped with stirring
With heating in water bath to 80 DEG C, open stirring, mixed solution I and mixed solution II are simultaneously added dropwise in four-hole bottle, dropping
Time is 0.7h, drips complete follow-up continuous stirring 50min, carries out crystallization 40h at 70 DEG C, be washed with deionized to
Filtering after neutrality, filter cake is in 65 DEG C of drying, cooling, and broken, screening obtains catalyst precarsor.Catalyst precarsor normal pressure,
In 250 DEG C of roasting 4h under logical nitrogen protection, then at 300 DEG C, process 40h by anhydrous HF, obtain fluorination catalyst.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) is configured to 300mL mixed solution I with deionized water, by sodium hydroxide
35.00g and sodium carbonate 7.5g deionized water are configured to 300mL mixed solution II, standby.To the 500ml equipped with stirring
Four-hole bottle adds the deionized water of 60mL, then by four-hole bottle heating in water bath to 90 DEG C, opens stirring, will mixing
Solution I and mixed solution II are simultaneously added dropwise in four-hole bottle, and time for adding is 0.9h, drip complete follow-up continuous stirring
55min, carries out crystallization 48h at 80 DEG C, is washed with deionized to neutrality filtration, and filter cake is in 70 DEG C of drying, cold
But, broken, screening obtains catalyst precarsor.Catalyst precarsor under normal pressure, the protection of logical nitrogen in 400 DEG C of roasting 6h,
At 450 DEG C, process 6h by anhydrous HF again, obtain fluorination catalyst.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) prepares with deionized water
Become 300mL mixed solution I, sodium hydroxide 43.00g and sodium carbonate 9.39g deionized water are configured to 300mL and mix
Close solution II, standby.The deionized water of 35mL is added, then by four-hole bottle in the 500ml four-hole bottle equipped with stirring
With heating in water bath to 100 DEG C, open stirring, mixed solution I and mixed solution II are simultaneously added dropwise in four-hole bottle, drip
Adding the time is 1.2h, drips complete follow-up continuous stirring 60min, carries out crystallization 6h, be washed with deionized at 90 DEG C
Filtering to neutrality, filter cake is in 85 DEG C of drying, cooling, and broken, screening obtains catalyst precarsor.Catalyst precarsor is often
In 450 DEG C of roasting 5h under pressure, logical nitrogen protection, then at 500 DEG C, process 12h by anhydrous HF, obtain 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·H2O
9.50g(0.03mol)、Mg(NO3)2·6H2O 92.30g(0.36mol)、Zn(NO3)2·5H2O 107.10g(0.36mol)
It is configured to 300mL mixed solution I, by sodium hydroxide 43.00g and sodium carbonate 9.39g deionized water with deionized water
It is configured to 300mL mixed solution II, standby.The deionization of 45mL is added in the 500ml four-hole bottle equipped with stirring
Water, then by four-hole bottle heating in water bath to 85 DEG C, opens stirring, mixed solution I and mixed solution II is simultaneously added dropwise
In four-hole bottle, time for adding is 1.5h, drips complete follow-up continuous stirring 45min, carries out crystallization 12h at 100 DEG C,
Being washed with deionized to neutrality filtration, filter cake is in 90 DEG C of drying, cooling, and broken, screening obtains catalyst precarsor.
Catalyst precarsor in 500 DEG C of roasting 2h, then processes 30h by anhydrous HF under normal pressure, the protection of logical nitrogen at 350 DEG C,
Obtain fluorination catalyst.Its reactivity and selectivity are shown in Tables 1 and 2.
The catalyst that table 1 embodiment 1-6 the prepares activity to HCFC133a and the selectivity of HFC134a
(HF:HCFCl33a=8:1, air speed: 2500h-1, product, after washing alkali cleaning, detects with GC)
Long-lasting catalytic that table 2 embodiment 1-6 prepares use after to the activity of HCFC133a and the choosing of HFC134a
Selecting property (HF:HCFCl33a=8:1, air speed: 2500h-1, product, after washing alkali cleaning, detects with GC).
Claims (8)
1. the catalyst precarsor synthesizing HFA 134a, it is characterised in that described catalyst precarsor is that one is many
Unit's houghite, its chemical composition is [M2+ 1-xM3+ x(OH)2]x+(An- x/n)·mH2O, wherein: M2+And M3+Represent respectively
Bivalence and trivalent metal ion, An-Representing anion, x is M3+/(M2++M3+) mol ratio, n is 1 or 2 or 3,
M is 0.3-0.7.
The catalyst precarsor of synthesis HFA 134a the most according to claim 1, it is characterised in that described
M2+For Mg2+、Mn2+、Co2+、Ni2+And Zn2+In one or more, described M3+For Cr3+Or Cr3+With Al3+
Or In3+In the mixture of at least one, described An-It is CO3 2-、OH-、NO3 -In one or more, described
X be 0.1-0.5.
3. use the method that the catalyst precarsor described in claim 1 prepares catalyst, it is characterised in that include following step
Rapid:
(1) trivalent metal salt and divalent metal salt are configured to mixed solution I with deionized water by a certain percentage；Will
NaOH and Na2CO3It is configured to mixed solution II by a certain percentage with deionized water；
(2) mixed solution I and the mixed solution II step (1) obtained is simultaneously added dropwise in deionized water, drips
At 60-100 DEG C, react 30-60min after Biing, then at 60-100 DEG C, carry out crystallization 6-48h, wash and filter to neutrality,
Filter cake, in 60-90 DEG C of drying, cooling, crushes, and screening obtains catalyst precarsor；
(3) catalyst precarsor obtained by step (2) is led to nitrogen protective roast 2-8h, sintering temperature at ambient pressure
200-500 DEG C, then lead to anhydrous HF activation processing 6-48h, activation temperature 200-500 DEG C, obtain fluorination catalyst.
Preparation method the most according to claim 3, it is characterised in that in the mixed solution I described in step (1),
The molal quantity of bivalent metal ion is 2-4:1 with the ratio of the molal quantity of trivalent metal ion.
Preparation method the most according to claim 3, it is characterised in that in the mixed solution I described in step (1),
Cr3+The ratio of molal quantity and the total mole number of trivalent metal ion be 0.1-1:1.
Preparation method the most according to claim 3, it is characterised in that in the mixed solution II described in step (1),
NaOH and Na2CO3Mass ratio is 4-10:1.
Preparation method the most according to claim 3, it is characterised in that the mixed solution I described in step (2) is with mixed
Closing the cumulative volume of solution II with the ratio of the volume of deionized water is 10-20:1.
Preparation method the most according to claim 3, it is characterised in that the time for adding described in step (2) is 0.5-1.5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511021892.4A CN105936515B (en) | 2015-12-30 | 2015-12-30 | A kind of preparation method for the catalyst precarsor and catalyst for synthesizing 1,1,1,2 HFC-134as |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511021892.4A CN105936515B (en) | 2015-12-30 | 2015-12-30 | A kind of preparation method for the catalyst precarsor and catalyst for synthesizing 1,1,1,2 HFC-134as |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105936515A true CN105936515A (en) | 2016-09-14 |
| CN105936515B CN105936515B (en) | 2017-10-24 |
Family
ID=57153013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201511021892.4A Active CN105936515B (en) | 2015-12-30 | 2015-12-30 | A kind of preparation method for the catalyst precarsor and catalyst for synthesizing 1,1,1,2 HFC-134as |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105936515B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565412A (en) * | 2016-11-08 | 2017-04-19 | 衢州学院 | Device and method for preparing 1,1,1,2-tetrafluoroethane |
| CN107376952A (en) * | 2017-06-09 | 2017-11-24 | 浙江三美化工股份有限公司 | A kind of preparation method of HFC-134a 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1268501A (en) * | 1999-03-30 | 2000-10-04 | 郭荔 | Method for simultaneously producing pentafluoroethane and tetrafluorochloroethane |
| US6403524B2 (en) * | 1996-09-10 | 2002-06-11 | Imperial Chemical Industries Plc | Fluorination catalyst and process |
| CN1792449A (en) * | 2005-12-06 | 2006-06-28 | 北京化工大学 | Aluminium-based pseudo-hydrotalcite structuralization catalyst, and its prepn. method |
| CN1820845A (en) * | 2005-09-30 | 2006-08-23 | 山东东岳化工股份有限公司 | Iron series chromium base catalyst for 1,1,1,2-tetrafluoro ethane |
-
2015
- 2015-12-30 CN CN201511021892.4A patent/CN105936515B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6403524B2 (en) * | 1996-09-10 | 2002-06-11 | Imperial Chemical Industries Plc | Fluorination catalyst and process |
| CN1268501A (en) * | 1999-03-30 | 2000-10-04 | 郭荔 | Method for simultaneously producing pentafluoroethane and tetrafluorochloroethane |
| CN1820845A (en) * | 2005-09-30 | 2006-08-23 | 山东东岳化工股份有限公司 | Iron series chromium base catalyst for 1,1,1,2-tetrafluoro ethane |
| CN1792449A (en) * | 2005-12-06 | 2006-06-28 | 北京化工大学 | Aluminium-based pseudo-hydrotalcite structuralization catalyst, and its prepn. method |
Non-Patent Citations (4)
| Title |
|---|
| 吕亮等: "水滑石的制备、表征及其在酯交换反应中的应用", 《精细石油化工》 * |
| 程永香: "Cr基催化剂上气相氟化四氯乙烯合成五氟乙烷性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 钱林等: "气相氟化合成1,1,1,2-四氟乙烷的CrOx-Y2O3 催化剂的表征与性能", 《物理化学学报》 * |
| 韩银凤: "高结晶性镍铁层状双金属氢氧化物的合成及表征研究", 《中国优秀硕士论文全文数据库 工程科技I辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565412A (en) * | 2016-11-08 | 2017-04-19 | 衢州学院 | Device and method for preparing 1,1,1,2-tetrafluoroethane |
| CN107376952A (en) * | 2017-06-09 | 2017-11-24 | 浙江三美化工股份有限公司 | A kind of preparation method of HFC-134a catalyst |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105936515B (en) | 2017-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2794093B1 (en) | Zinc and manganese aluminate catalyst useful for alkane dehydrogenation | |
| TW200530212A (en) | ||
| CN104549360B (en) | Catalyst for producing chlorine by catalytic oxidation of hydrogen chloride | |
| JP5716669B2 (en) | Methanol synthesis catalyst | |
| CN105936515B (en) | A kind of preparation method for the catalyst precarsor and catalyst for synthesizing 1,1,1,2 HFC-134as | |
| CN109180420A (en) | A kind of preparation method of 1,1- difluoroethylene | |
| MX2010012555A (en) | A process for dehydrochlorinating 1,1,1,2-tetrafluoro-2-chloropro pane to 2,3,3,3-tetrafluoropropene in the presence of an alkali metal-doped magnesium oxyfluoride catalyst and methods for making the catalyst. | |
| CN104105681A (en) | Process for producing fluorine-containing olefin | |
| CN100998942A (en) | Ethylene oxychlorination catalyst and its preparation method and application | |
| CN105503544A (en) | Method for catalytically synthesizing propylene glycol methyl ether by adopting solid base catalyst KF/ZrO2-SiO2 | |
| CN104707631A (en) | Chromium-free gas phase fluorination catalyst and use thereof | |
| CN102836722A (en) | Catalyst used in preparation of fluorine-containing olefin through dehydrohalogenation of halohydrofluoroalkane and preparation method of catalyst | |
| CN105879892A (en) | Solid base catalyst for synthesizing dimethyl carbonate through transesterification method and preparation method and application | |
| CN107952436B (en) | Copper-zirconium-based catalyst for preparing chlorine by oxidizing hydrogen chloride and preparation method and application thereof | |
| WO2022028236A1 (en) | Method for synthesizing difluoromethane by means of gas phase catalysis | |
| CN100444958C (en) | Fluorination catalyst, its prepn. method and use | |
| CN105562058B (en) | A kind of catalyst for synthesizing 2,3,3,3 tetrafluoropropenes and preparation method thereof | |
| CN112246236B (en) | Low-carbon alkane chromium-based dehydrogenation catalyst containing spinel structure and preparation method thereof | |
| CN108047040A (en) | A kind of method of ethylene carbonate and alcohols one-step synthesis carbonic acid symmetrical ester | |
| CN111499489B (en) | Isomerization method of fluorine-containing olefin | |
| CN107635954A (en) | Use the method for hypoergia adsorbent purification hydrocarbon flow | |
| CN105772108B (en) | A kind of methane synthesizing catalyst layered vector and preparation method thereof | |
| JPH02188542A (en) | Production of phenol | |
| CN105727923B (en) | A kind of catalyst for synthesizing HFC-125 and preparation method thereof | |
| CN102614901B (en) | Catalyst for synthesizing 2-chloro-3,3,3-trifluoropropene from 1,1,2,3-tetrachloropropylene and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
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 |