CN103896213A - Method for purifying hydrogen chloride by adopting anhydrous calcium chloride - Google Patents
Method for purifying hydrogen chloride by adopting anhydrous calcium chloride Download PDFInfo
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- CN103896213A CN103896213A CN201210580615.7A CN201210580615A CN103896213A CN 103896213 A CN103896213 A CN 103896213A CN 201210580615 A CN201210580615 A CN 201210580615A CN 103896213 A CN103896213 A CN 103896213A
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Abstract
The invention discloses a method for purifying hydrogen chloride by adopting anhydrous calcium chloride. According to the method, by adopting the anhydrous calcium chloride as an HF adsorbing agent, a hydrogen chloride gas to be treated is purified by using the following chemical reaction: (2HF+CaCl2->CaF2+2HCl), wherein the anhydrous calcium chloride is activated, the reaction temperature is -40-50 DEG C, the reaction pressure is 0.1-5MPa, and the reaction time is 6min -18 hours. According to the method, the hydrogen chloride gas is purified through a chemical reaction of the anhydrous calcium chloride and a hydrogen fluoride gas, the concentration of the hydrogen fluoride gas is reduced to be less than 10 ppm, and thus recovering and recycling of high-purity hydrogen chloride are realized; and the method is especially suitable for recycling the hydrogen chloride as a byproduct generated in a process of producing fluorides such as tetrafluoroethane, and is remarkable in environment and economic values.
Description
Technical field
The technique of hydrogenchloride the present invention relates to purify, specifically, relate to a kind of method that uses hydrogen fluoride gas in the hydrogen chloride gas of Calcium Chloride Powder Anhydrous place to go, the concentration that finally realizes hydrogen fluoride gas is less than 10ppm, thereby has realized the recovery and reuse of high purity chlorination hydrogen.
Background technology
R 134a is a kind of R-12(of replacement methyl chlorofluoride) HFC class refrigeration agent, its Chemical Composition is Tetrafluoroethane.R 134a can be applicable to the fixed business refrigeration system of novel middle high temperature, as handpiece Water Chilling Units and Domestic refrigerator.In addition, can also be used for replacing existing R-12 refrigeration system and air-conditioning system.Also be the global standards of new mobile type air-conditioning simultaneously, can be used for replacing existing R-12 movable air conditioner system.
R-134a is as most popular middle low-temperature environment-friendly refrigeration agent, due to its good over-all properties:
(1) do not damage the ozone layer, not chloride element in its molecular formula, therefore its depletion of the ozone layer latent energy value (ODP) is 0, Global warming coefficient value (GWP) is less than 0.2;
(2) toxicity is extremely low, permissible concentration and R22(difluorochloromethane) same, be all 1000ppm;
(3) non-combustible, airborne flammable polarity is 0;
(4) chemistry and thermostability are high;
(5) moisture solvability and R22 are almost identical;
(6) be mix refrigerant, formed by two kinds of refrigeration agents;
(7) do not mix with mineral oil or alkylbenzene oil, with ester oil grease POE(Poly Olefin Elastomer, the elastomerics of polyolefins), ether lubricating oil PVE(Polyvinyl ether, polyethylene fat) mix.
Thereby; making R-134a become a kind of very effective and safe CFC-12(is R12) substitute; be mainly used in the most fields that use R12 refrigeration agent; comprise: in the refrigeration equipments such as refrigerator, refrigerator, water dispenser, automative air conditioning, central air-conditioning, dehumidifier, freezer, business refrigeration, frozen water machine, ice cream maker, refrigerated condensation unit; also can be applicable to aerosol propellant, medicinal aerosol, pesticide propellent, polymkeric substance (plastics) pneumatogen simultaneously, and Mg etc.
It is raw material that the production of R-134a adopts trieline and anhydrous hydrogen fluoride conventionally, through two step gas phase catalytic fluorination reactions, generates Tetrafluoroethane (be R-134a, make again HFC-134a).In its production process, can produce a large amount of hydrogen chloride gas, recyclable recycling, but contain micro-hydrogen fluoride gas in the hydrogen chloride gas obtaining in this process.As everyone knows, the hydrogen chloride gas that contains fluorochemical or hydrochloric acid, even if the content of fluorochemical is extremely low, also can exceed certain permissible concentration standard, thereby make hydrogenchloride or hydrochloric acid lose economic worth.For example, fluoride concn is more than 50ppm, and hydrochloric acid just may etching glass and enamel.Therefore, by the content of fluorochemical be reduced to acceptable scope (as, lower than 50ppm) will solve potential production problem and produce economic worth.But, due to hydrogen fluoride and hydrogenchloride homomorphosis, be difficult to separate with usual method.
Summary of the invention
The object of this invention is to provide a kind of hydrofluoric processing method of removing in anhydrous hydrogen chloride gas, can fast and effeciently remove hydrogen fluoride, make its content in hydrogenchloride lower than 10ppm, make hydrogenchloride can be applicable to industrial circle.
In order to achieve the above object, the invention provides a kind of Calcium Chloride Powder Anhydrous method for purifying hydrogen chloride that adopts, it is characterized in that, it is HF sorbent material that described method adopts Calcium Chloride Powder Anhydrous, utilizes the following chemical reaction pending hydrogen chloride gas of purifying:
2HF ＋ CaCl
2 → CaF
2 ＋ 2HCl
Wherein, described Calcium Chloride Powder Anhydrous is activated processed; Temperature of reaction is-40 ℃ ~ 50 ℃; Reaction pressure is 0.1MPa ~ 5Mpa, and the reaction times is 6min ~ 18h.
Above-mentioned employing Calcium Chloride Powder Anhydrous method for purifying hydrogen chloride, wherein, described poling processing technique is the baking 1-5h of high temperature 300-400 ℃.
Above-mentioned employing Calcium Chloride Powder Anhydrous method for purifying hydrogen chloride, wherein, described poling processing technique is to toast under the condition of vacuum.
Above-mentioned employing Calcium Chloride Powder Anhydrous method for purifying hydrogen chloride, wherein, described Calcium Chloride Powder Anhydrous refers to that after activation treatment, also through comminution by gas stream, the particle diameter obtaining is the calcium chloride of 1-50 micron.
Above-mentioned calcium chloride through dewatering, pulverization process so that remove the material adsorbing in calcium chloride, avoid impurity to be brought in hydrogen chloride gas, meanwhile, the calcium chloride particulate after pulverizing, contact area improves, and can accelerate calcium chloride and hydrofluoric speed of response.
Above-mentioned employing Calcium Chloride Powder Anhydrous method for purifying hydrogen chloride, wherein, described temperature of reaction is 50 ℃, pressure is 5Mpa.
Above-mentioned employing Calcium Chloride Powder Anhydrous method for purifying hydrogen chloride, wherein, described pending hydrogen chloride gas is the hydrofluoric hydrogen chloride gas containing more than 1000ppm.
The present invention adopts the chemical reaction purification hydrogen chloride gas of Calcium Chloride Powder Anhydrous and hydrogen fluoride gas, and the concentration that finally realizes hydrogen fluoride gas is less than 10ppm, thereby has realized the recovery and reuse of high purity chlorination hydrogen, has significant environment and economy and is worth.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described.Should be understood that following examples are only for the present invention is described but not for limiting the scope of the invention.
Embodiment 1-10
The Calcium Chloride Powder Anhydrous that embodiment adds 100g to activate in 500mL pressure reaction still, then the hydrogen chloride gas that is 1000ppm by hydrogen fluoride concentration passes into reactor, and control reactor pressure 0.1 to 5MPa, reflection temperature-40 are ℃ within the scope of 200 ℃, reaction times is 5min-18h, specifically as shown in table 1:
Table 1: the reaction conditions of embodiment 1-10 and result
Wherein, the subscript 1 of concentration represents the concentration of the HF of reaction 1min; The subscript 2 of concentration represents the concentration of the HF of reaction 10min.
As described in above-described embodiment and table 1, can find out, reactor pressure 0.1MPa ~ 5Mpa, temperature of reaction is-40 ℃ ~ 200 ℃, reaction times is under the processing condition of 6 minutes-18 hours, HF concentration can be purified to HF concentration at the hydrogenchloride of 1000ppm left and right and be low to moderate 10ppm, make the hydrogenchloride after purifying can be applied to safely industrial circle, the recycling that is specially adapted to produce the byproduct hydrogen chloride producing in the fluorochemical techniques such as Tetrafluoroethane.
Although content of the present invention has been done detailed introduction by above preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.Read after foregoing those skilled in the art, for multiple modification of the present invention and substitute will be all apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (6)
1. adopt a Calcium Chloride Powder Anhydrous method for purifying hydrogen chloride, it is characterized in that, it is HF sorbent material that described method adopts Calcium Chloride Powder Anhydrous, utilizes the following chemical reaction pending hydrogen chloride gas of purifying:
2HF ＋ CaCl
2 → CaF
2 ＋ 2HCl
Wherein, described Calcium Chloride Powder Anhydrous is activated processed; Temperature of reaction is-40 ℃ ~ 50 ℃; Reaction pressure is 0.1MPa ~ 5Mpa, and the reaction times is 6min ~ 18h.
2. employing Calcium Chloride Powder Anhydrous method for purifying hydrogen chloride as claimed in claim 1, is characterized in that, described poling processing technique is the baking 1-5h of high temperature 300-400 ℃.
3. employing Calcium Chloride Powder Anhydrous method for purifying hydrogen chloride as claimed in claim 2, is characterized in that, described poling processing technique is to toast under the condition of vacuum.
4. the employing Calcium Chloride Powder Anhydrous method for purifying hydrogen chloride as described in any one in claim 1-3, is characterized in that, described Calcium Chloride Powder Anhydrous refers to that after activation treatment, also through comminution by gas stream, the particle diameter obtaining is the calcium chloride of 1-50 micron.
5. employing Calcium Chloride Powder Anhydrous method for purifying hydrogen chloride as claimed in claim 4, is characterized in that, described temperature of reaction is 50 ℃, and pressure is 5Mpa.
6. employing Calcium Chloride Powder Anhydrous method for purifying hydrogen chloride as claimed in claim 5, is characterized in that, described pending hydrogen chloride gas is the hydrofluoric hydrogen chloride gas containing more than 1000ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210580615.7A CN103896213A (en) | 2012-12-28 | 2012-12-28 | Method for purifying hydrogen chloride by adopting anhydrous calcium chloride |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210580615.7A CN103896213A (en) | 2012-12-28 | 2012-12-28 | Method for purifying hydrogen chloride by adopting anhydrous calcium chloride |
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| CN103896213A true CN103896213A (en) | 2014-07-02 |
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| CN201210580615.7A Pending CN103896213A (en) | 2012-12-28 | 2012-12-28 | Method for purifying hydrogen chloride by adopting anhydrous calcium chloride |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104128162A (en) * | 2014-07-02 | 2014-11-05 | 浙江巨化股份有限公司 | Load-type fluorine remover used for removing hydrogen fluoride in hydrogen chloride gas and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3976447A (en) * | 1973-04-26 | 1976-08-24 | Pennwalt Corporation | Removal of hydrogen fluoride from gaseous mixture by absorption on alkaline earth metal fluoride |
| US4009214A (en) * | 1975-04-25 | 1977-02-22 | The Lummus Company | Separation of hydrogen fluoride from hydrogen chloride gas |
| US4128626A (en) * | 1971-06-16 | 1978-12-05 | Pennwalt Corporation | Purification of gaseous hydrogen chloride |
| US4154804A (en) * | 1977-12-22 | 1979-05-15 | Allied Chemical Corporation | Novel calcium chloride scrubbing bath |
-
2012
- 2012-12-28 CN CN201210580615.7A patent/CN103896213A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4128626A (en) * | 1971-06-16 | 1978-12-05 | Pennwalt Corporation | Purification of gaseous hydrogen chloride |
| US3976447A (en) * | 1973-04-26 | 1976-08-24 | Pennwalt Corporation | Removal of hydrogen fluoride from gaseous mixture by absorption on alkaline earth metal fluoride |
| US4009214A (en) * | 1975-04-25 | 1977-02-22 | The Lummus Company | Separation of hydrogen fluoride from hydrogen chloride gas |
| US4154804A (en) * | 1977-12-22 | 1979-05-15 | Allied Chemical Corporation | Novel calcium chloride scrubbing bath |
Non-Patent Citations (4)
| Title |
|---|
| 刘荣贵等: "《五金交电化工建材商品实用手册-化工涂料篇》", 31 May 1995, article "11.1.4 无水氯化钙" * |
| 陈嘉庚等: "《家用、商用电冰箱和小型冷库的制冷维修技术》", 28 February 1990, article "（3）干燥剂、制冷剂的脱水处理" * |
| 陈稀等: "《化学纤维实验教程》", 31 December 1988, article "三、仪器和试剂" * |
| 黄文镛等: "《备用锅炉防腐》", 30 June 1958, article "第一节 无水氯化钙法" * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104128162A (en) * | 2014-07-02 | 2014-11-05 | 浙江巨化股份有限公司 | Load-type fluorine remover used for removing hydrogen fluoride in hydrogen chloride gas and preparation method thereof |
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Address after: 200433 10007C room, No. 335, National Road, Shanghai, Yangpu District Applicant after: SHANGHAI MASTECH ENVIRONMENT CO., LTD. Address before: 200433, room 490, country road 1102, Shanghai, Yangpu District Applicant before: Shanghai Masteck Ecology Science & Technology Co., Ltd. |
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Application publication date: 20140702 |