CN105107531A - Catalyst for synthesizing sulfuryl fluoride and preparation method therefor - Google Patents
Catalyst for synthesizing sulfuryl fluoride and preparation method therefor Download PDFInfo
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- CN105107531A CN105107531A CN201510509152.9A CN201510509152A CN105107531A CN 105107531 A CN105107531 A CN 105107531A CN 201510509152 A CN201510509152 A CN 201510509152A CN 105107531 A CN105107531 A CN 105107531A
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Abstract
The invention discloses a catalyst for synthesizing sulfuryl fluoride. The catalyst is characterized in that columnar activated charcoal serves as a support of the catalyst and supports alkali metal fluoride; and the catalyst has the following parameters that the moisture content is lower than 5%, the specific surface area is higher than 1,000m<2>/g, the wear-resisting strength is higher than 90%, the bulk specific weight is 350-400kg/m<3>, the iodine number is 950-970mg/g, the mass content of the alkali metal fluoride is 12-17%, and the diameter of the columnar activated charcoal is smaller than 4mm. A preparation method for the catalyst comprises the steps of preparing an aqueous solution from the alkali metal fluoride, soaking the columnar activated charcoal in the aqueous solution for 12-16 hours in accordance with that the weight ratio of the columnar activated charcoal to the alkali metal fluoride is 1: (0.14-0.25), and then, carrying out drying. According to the catalyst disclosed by the invention, the selective conversion ratio of the raw materials for synthesizing sulfuryl fluoride can be greatly increased, the catalytic productivity of the catalyst of unit weight is also greatly improved, and the reaction time for synthesizing sulfuryl fluoride is shortened; and the preparation process for the catalyst disclosed by the invention is simple and convenient and is suitable for industrial production.
Description
Technical field
The invention belongs to chemical industry synthesis field, particularly a kind of catalyst for the synthesis of vikane and use this catalyst to synthesize the method for vikane.
Technical background
Vikane (SO
2f
2), be no color or smell gas under normal temperature and pressure, because it has that diffusion permeability is strong, broad spectrum disinfestation, dosage are economized, residual quantity is low, desinsection speed fast, the loose gas time is short, low temperature is easy to use, does not affect germination percentage and the feature such as toxicity is lower, be applied to warehouse, freighter, container and building, reservoir dam, termite control and gardens more and more widely and survive the winter the control of insect, the tree moth dryness insect that lives.Do not damage the ozone layer due to it, so it is a kind of desirable alternative methyl bromide environmental protection fumigant simultaneously.The vikane preparation were established of current report mainly contains following 5 kinds: 1. with the direct flaorination process that sulfur dioxide and fluorine are raw material; 2. with the nitrosyl fluoride technique that sulfur dioxide and nitrosyl fluoride are raw material; 3. with the fluosulfonic acid technique that fluosulfonic acid and barium chloride are raw material; 4. with the barium fluosilicate technique that barium sulphide and sulfur trioxide etc. are raw material; 5., with sulfur dioxide, chlorine and anhydrous hydrofluoric acid are the technique of raw material.Comparatively speaking, process route 5 has low raw-material cost, and reaction condition is gentle, and the features such as technological operation is simple, are generally adopted in the industrial production.4 kinds of methods do not have commercial value above.China just starts to manufacture experimently vikane the beginning of the eighties.Technique 5 synthetic route is as follows:
Chlorination reaction:
SO
2+C1
2→SO
2C1
2
Fluorination reaction:
The method is gas-phase reaction.Catalyst used mainly contains active carbon, charcoal carries palladium etc.In the U.S.'s three sections of patents, (US2772144, US3092458, US4102987) just teaches a kind of charcoal that uses and carries palladium for catalyst, the synthesis technique of sulfur dioxide, chlorine and hydrogen fluoride gaseous mixture phase continuous reaction.But because catalyst target product selectivity is poor, the more difficult separation of accessory substance of generation, and also catalyst easy inactivation catalytic efficiency is low, and catalyst cost is high, so adopt this catalyst still can not adapt to suitability for industrialized production.
Summary of the invention
In order to overcome above-mentioned defect of the prior art, the invention provides a kind of catalyst for the synthesis of vikane, its outstanding advantages is: feed stock conversion and selectivity of product high, catalyst life is long.
Object of the present invention is achieved through the following technical solutions:
For the synthesis of a catalyst for vikane, it is characterized in that, the carrier of described catalyst is column-shaped active carbon, carrying alkali metal fluoride on it; The parameter of described catalyst is as follows: moisture < 5%; Specific area>=1000m
2/ g; Scuff resistance>=90%; Bulk density is 350 ~ 400kg/m3, and iodine number is 950 ~ 970mg/g; Alkali metal fluoride mass content is 12% ~ 17%; The diameter < 4mm of column-shaped active carbon; The preparation method of described catalyst is: alkali metal fluoride is configured to the aqueous solution, is the ratio of 1 ︰ 0.14 ~ 0.25 in column-shaped active carbon and alkali metal fluoride weight ratio, is soaked by column-shaped active carbon after 12-16 hour dry in aqueous.
Further, alkali metal fluoride is potassium fluoride or potassium hydrogen fluoride.
The diameter of column-shaped active carbon is preferably 3mm.
Alkali metal fluoride content is preferably 17%.
Described catalyst pH value is faintly acid or neutrality.
Present invention also offers a kind of method using above-mentioned catalyst to synthesize vikane.
A kind of method of commercial synthesis vikane, it is characterized in that, comprise step: joined by catalyst in inside reactor tubulation, be warming up to 180 DEG C, pass into chlorine that mol ratio is 1 ︰ 1.2 ︰ 4, sulfur dioxide, hydrogen fluoride carries out chlorofluorination reaction, wherein the mass ratio of catalyst and chlorine is 1 ︰ 10 ~ 16, obtained target product vikane, the carrier of described catalyst is column-shaped active carbon, carrying alkali metal fluoride on it; The parameter of described catalyst is as follows: moisture < 5%; Specific area>=1000m
2/ g; Scuff resistance>=90%; Bulk density is 350 ~ 400kg/m3, and iodine number is 950 ~ 970mg/g; Alkali metal fluoride mass content is 12% ~ 17%; The diameter < 4mm of column-shaped active carbon; The preparation method of described catalyst is: alkali metal fluoride is configured to the aqueous solution, is the ratio of 1 ︰ 0.14 ~ 0.25 in column-shaped active carbon and alkali metal fluoride weight ratio, is soaked by column-shaped active carbon after 12-16 hour dry in aqueous.
In catalyst of the present invention, alkali metal fluoride accounts for more than 12% of whole catalyst quality content, and catalyst self specific area is not less than 950m
2/ g, pH value is faintly acid ~ neutrality, and bulk density is 350 ~ 400kg/m
3.Use catalyst of the present invention, average per kilogram catalyst can produce vikane product 22.34kg; Three kinds of raw material consumptions are chlorine 1.22, sulfur dioxide 1.05, hydrogen fluoride 0.79.The reaction yield of catalyst Unit Weight of the present invention is nearly 3 times of commercial catalyst product, achieves unexpected technique effect.
Catalyst of the present invention can make synthesis vikane raw material selective conversion rate greatly improve, the catalysis production capacity of Unit Weight catalyst also improves greatly, the synthesis vikane reaction time also shortens to some extent, and catalyst manufacture craft of the present invention is easy, is suitable for suitability for industrialized production.
Detailed description of the invention:
The preparation of catalyst:
Embodiment 1:
At 2.0m
3in Plastic Drum, add 45kg potassium fluoride, then slowly inject 1.2m
3water, stirs; This liquid is poured into fast and is equipped with in about 300kg column-shaped active carbon (particle diameter 4mm) another Plastic Drum, leave standstill active carbon natural air drying after 12 hours; Finally by the active carbon vacuum drying after air-dry.The catalyst of obtained binary system.
After testing, the parameters of catalyst is as follows:
Embodiment 2:
At 2.0m
3in Plastic Drum, add 77kg potassium fluoride, then slowly inject 1.5m
3water, stirs; This liquid is poured into fast and is equipped with in about 380kg column-shaped active carbon (particle diameter 3.5mm) another Plastic Drum, leave standstill active carbon natural air drying after 14 hours; Finally by the active carbon vacuum drying after air-dry.The catalyst of obtained binary system.
After testing, the parameters of catalyst is as follows:
Embodiment 3:
At 2.0m
3in Plastic Drum, add 87.5kg potassium fluoride, then slowly inject 1.5m
3water, stirs; This liquid is poured into fast and is equipped with in about 350kg column-shaped active carbon (particle diameter 3mm) another Plastic Drum, leave standstill active carbon natural air drying after 16 hours; Finally by the active carbon vacuum drying after air-dry.The catalyst of obtained binary system.
After testing, the parameters of catalyst is as follows:
The preparation of vikane:
Embodiment 4:
The binary catalyst 300kg that embodiment 1-3 is prepared, join in inside reactor tubulation, be warming up to 180 DEG C, pass into chlorine that mol ratio is 1 ︰ 1.2 ︰ 4, sulfur dioxide, hydrogen fluoride carries out chlorofluorination reaction, wherein Cuiization Ji ︰ chlorine=1 ︰ 14 (mass ratio), obtained target product vikane.Concrete course of reaction:
Gasification process:
This production system raw material has three kinds, respectively: chlorine, sulfur dioxide, hydrogen fluoride.Chlorine and sulfur dioxide are transported to our company by steel cylinder, then be depressed into respective measuring tank by feeding line; Can fill material 1t in single steel cylinder, measuring tank own volume is 1.5m
3, install single only corresponding steel cylinder when the material in each measuring tank is empty again additional, when installing raw material additional and produce, the material all controlled in measuring tank must not higher than 7KG pressure; Hydrogen fluoride beats to HF measuring tank from tank field by submerged pump, and fill into virgin material when measuring tank is empty, the single amount of filling into is 1t; Feed supplement and pressure when producing in control measuring tank must not higher than 1.5KG pressure.During production, beat to vaporizer by respective delivery pump, the delivery pump outlet pressure of three kinds of materials is at 3 ~ 5KG pressure, inventory is respectively: chlorine 200KG/h, sulfur dioxide 200KG/h, hydrogen fluoride 160KG/h, be vaporized by heat-conducting oil heating again, gasification temperature controls at 140 ~ 180 DEG C, and Stress control is at 3 ~ 5KG.Reactor is entered after gasification.
Reaction dust-removing process:
The material that mixing gasifying is good counts reactor, and under the condition of catalyst, heating, start reaction, reaction temperature controls at 180 ~ 230 DEG C, pressure 3 ~ 5KG.Reactor totally 3 groups, A B C cover, often overlap reactor 2 (series connection, increase reaction time).Completely reacted gaseous mixture first through cyclonic separation after bag-type dust filter, when cloth envelop collector inlet outlet pressure differential higher than during 100KPa change cloth bag, then enter hydrogen chloride refining step.
Hydrogen chloride refined material recovery process:
The advanced subcooler of completely reacted mixture cools (circulating water), enter No. 1 rectifying column again, do phegma with product vikane and refine hydrogen chloride, same vikane refluxes purified product, in control rectifying column condenser, refrigerant liquid level is between 70 ~ 100cm, rectifier column reflux point megadyne temperature degree-20 ~-35 DEG C, pressure 2 ~ 4KG in rectifying column, tower reactor liquid level 50 ~ 70cm, hydrogen chloride and the top discharge of product vikane are to the adsorbing chlorinated hydrogen of falling-film tower, rectifying column pressure at expulsion controls at 20 ~ 50KPa, top vikane is through water scrubber, caustic wash tower deacidifies, enter compression rectification section.Other accessory substance of bottom and unreacted raw material pass through No. 3 rectifying column rectifying again to Ethylene recov temporary tank V0134, and in V0134, mixed liquor is mainly hydrogen fluoride, with transport pump to hydrogen fluoride measuring tank.Control rectifying column column bottom temperature 30 ~ 50 DEG C, liquid level 50 ~ 70cm, pressure 2 ~ 4KG in tower; In control V0134, weight of material is lower than 4.5t, and pressure is lower than 3KG.
Thick product drying rectification working process:
Mixed material after the process of water caustic wash tower enters cyclone separator V0161, freezing whirlwind dehydrater V0160, deep cooling cooling de-watering device enters dashpot V0159 and after X0168 drying dewaters, enters compressor C0170 again compress after dewatering, and is compressed to thick product groove V0172; Thick product groove V0172 intermittence is fed to rectifying column T0176AB, through the final rectifying of the preliminary rectifying of T0176 laggard rectifying column T0113B, enters product groove V0179 after rectifying is good after X0178 drying.Conversion ratio reaches more than 90% as calculated.
Embodiment 5: contrast test
Adopt the catalyst of embodiment 1-3 and commercially available sheet coconut husk charcoal to carry Compounds Catalyzed by Potassium Fluoride agent, catalysis vikane synthetic reaction, course of reaction is identical with embodiment 4.Result is as following table:
From comparative test result,
1, as seen from the above table: commercially available sheet coconut carbon carries Compounds Catalyzed by Potassium Fluoride agent, average per kilogram can produce vikane product 8.01kg; Three kinds of raw material consumptions are chlorine 1.64, sulfur dioxide 1.67, hydrogen fluoride 1.15.
Embodiment of the present invention 1-3 catalyst, average per kilogram can produce vikane product 22.34kg; Three kinds of raw material consumptions are chlorine 1.22, sulfur dioxide 1.05, hydrogen fluoride 0.79.
2, reach a conclusion from statistics, the reaction yield of catalyst Unit Weight of the present invention is nearly 3 times of commercial catalyst product, achieves unexpected technique effect.
Claims (6)
1. for the synthesis of a catalyst for vikane, it is characterized in that, the carrier of described catalyst is column-shaped active carbon, carrying alkali metal fluoride on it; The parameter of described catalyst is as follows: moisture < 5%; Specific area >=1000 ㎡/g; Scuff resistance >=90%; Bulk density is 350 ~ 400kg/m3, and iodine number is 950 ~ 970mg/g; Alkali metal fluoride mass content is 12% ~ 17%; The diameter < 4mm of column-shaped active carbon; The preparation method of described catalyst is: alkali metal fluoride is configured to the aqueous solution, is the ratio of 1 ︰ 0.14 ~ 0.25 in column-shaped active carbon and alkali metal fluoride weight ratio, is soaked by column-shaped active carbon after 12-16 hour dry in aqueous.
2. the catalyst for the synthesis of vikane according to claim 1, is characterized in that, alkali metal fluoride is potassium fluoride or potassium hydrogen fluoride.
3. the catalyst for the synthesis of vikane according to claim 1, is characterized in that, the diameter of column-shaped active carbon is 3mm.
4. the catalyst for the synthesis of vikane according to claim 3, is characterized in that, alkali metal fluoride content is 17%.
5. the catalyst for the synthesis of vikane according to claim 4, is characterized in that, described catalyst pH value is faintly acid or neutrality.
6. the method for a commercial synthesis vikane, it is characterized in that, comprise step: joined by catalyst in inside reactor tubulation, be warming up to 180 DEG C, pass into chlorine that mol ratio is 1 ︰ 1.2 ︰ 4, sulfur dioxide, hydrogen fluoride carries out chlorofluorination reaction, wherein the mass ratio of catalyst and chlorine is 1 ︰ 10 ~ 16, obtained target product vikane, the carrier of described catalyst is column-shaped active carbon, carrying alkali metal fluoride on it; The parameter of described catalyst is as follows: moisture < 5%; Specific area >=1000 ㎡/g; Scuff resistance >=90%; Bulk density is 350 ~ 400kg/m3, and iodine number is 950 ~ 970mg/g; Alkali metal fluoride mass content is 12% ~ 17%; The diameter < 4mm of column-shaped active carbon; The preparation method of described catalyst is: alkali metal fluoride is configured to the aqueous solution, is the ratio of 1 ︰ 0.14 ~ 0.25 in column-shaped active carbon and alkali metal fluoride weight ratio, is soaked by column-shaped active carbon after 12-16 hour dry in aqueous.
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| CN201510509152.9A CN105107531A (en) | 2015-08-19 | 2015-08-19 | Catalyst for synthesizing sulfuryl fluoride and preparation method therefor |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115744843A (en) * | 2022-10-28 | 2023-03-07 | 福建德尔科技股份有限公司 | High-efficiency synthesis system of fluorinated nitroxyl |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3320030A (en) * | 1963-06-24 | 1967-05-16 | Allied Chem | Production of sulfuryl fluoride |
| US4102987A (en) * | 1975-09-25 | 1978-07-25 | The Dow Chemical Company | Process for preparing sulfuryl-fluoride and -chlorofluoride products |
| CN1259515A (en) * | 1998-11-11 | 2000-07-12 | 索尔微氟及衍生物有限公司 | Method for sulfonic acid fluorine |
| CN1678520A (en) * | 2002-08-23 | 2005-10-05 | 索尔韦公司 | Process for preparing SO2F2 and SO2CLF |
| CN103864022A (en) * | 2012-12-13 | 2014-06-18 | 中化蓝天集团有限公司 | Sulfuryl fluoride preparation method |
-
2015
- 2015-08-19 CN CN201510509152.9A patent/CN105107531A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3320030A (en) * | 1963-06-24 | 1967-05-16 | Allied Chem | Production of sulfuryl fluoride |
| US4102987A (en) * | 1975-09-25 | 1978-07-25 | The Dow Chemical Company | Process for preparing sulfuryl-fluoride and -chlorofluoride products |
| CN1259515A (en) * | 1998-11-11 | 2000-07-12 | 索尔微氟及衍生物有限公司 | Method for sulfonic acid fluorine |
| CN1678520A (en) * | 2002-08-23 | 2005-10-05 | 索尔韦公司 | Process for preparing SO2F2 and SO2CLF |
| CN103864022A (en) * | 2012-12-13 | 2014-06-18 | 中化蓝天集团有限公司 | Sulfuryl fluoride preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 胡宏武: "高效低度新型熏蒸剂", 《含氟材料》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115744843A (en) * | 2022-10-28 | 2023-03-07 | 福建德尔科技股份有限公司 | High-efficiency synthesis system of fluorinated nitroxyl |
| CN115744843B (en) * | 2022-10-28 | 2023-07-18 | 福建德尔科技股份有限公司 | Efficient synthesis system for fluorinated nitroxyl |
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Application publication date: 20151202 |
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