EP0879211A1 - Production de fluorure d'hydrogene a tres faible teneur en arsenic - Google Patents

Production de fluorure d'hydrogene a tres faible teneur en arsenic

Info

Publication number
EP0879211A1
EP0879211A1 EP96938820A EP96938820A EP0879211A1 EP 0879211 A1 EP0879211 A1 EP 0879211A1 EP 96938820 A EP96938820 A EP 96938820A EP 96938820 A EP96938820 A EP 96938820A EP 0879211 A1 EP0879211 A1 EP 0879211A1
Authority
EP
European Patent Office
Prior art keywords
hydrogen fluoride
arsenic
oxidizer
hydrogen
component
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.)
Withdrawn
Application number
EP96938820A
Other languages
German (de)
English (en)
Inventor
Paul Frederick Kunkel
Charles Lewis Redmon
Somanahalli Naranappa Subbanna
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell International Inc
Original Assignee
AlliedSignal Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by AlliedSignal Inc filed Critical AlliedSignal Inc
Publication of EP0879211A1 publication Critical patent/EP0879211A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/19—Fluorine; Hydrogen fluoride
    • C01B7/191—Hydrogen fluoride
    • C01B7/195—Separation; Purification

Definitions

  • This invention relates to a process for the preparation of hydrogen fluoride having a very low arsenic level More specifically, the invention provides a process in which indust ⁇ al grade anhydrous hydrogen fluo ⁇ de, or an intermediate product obtained during the hydrogen fluo ⁇ de manufactu ⁇ ng process, is contacted with an oxidizer in order to oxidize the arsenic impuritv to produce anhvdrous hvdrogen fluoride with a level of arsenic impurity that is at least less than two parts per billion or aqueous hydrogen fluo ⁇ de with a correspondingly low level of arsenic
  • a generally employed method for manufactu ⁇ ng hvdrogen fluo ⁇ de involves heating a mixture of fluorspar and sulfu ⁇ c acid
  • the initial crude hvdrogen fluo ⁇ de resulting from this process contains a vanety of impu ⁇ ties that are removed by distillation to provide technical, or indust ⁇ al, grade anhydrous hydrogen fluo ⁇ de
  • This indust ⁇ al grade anhydrous hvdrogen fluo ⁇ de still contains large quantities of impurities including arsenic
  • the amount of arsenic impu ⁇ ty generally about 10 to 500 parts per million, depends on the arsenic impurity of the fluorspar from which the hydrogen fluoride was produced
  • anhydrous hydrogen fluo ⁇ de and aqueous hydrogen fluo ⁇ de solutions are used as cleaning and etching agents for silicon wafers, circuit boards and high speed, high density chips for computers and optics
  • Arsenic impu ⁇ ty in the hydrogen fluo ⁇ de deposits arsenic on the electronic component that may cause its failure
  • aqueous hydrogen fluo ⁇ de arsenic impurities of less than one pan per billion
  • industry's arsenic impurity level requirements will be in the parts per trillion and parts per quadrillion range
  • 4,756,899 discloses contacting hydrogen fluoride with hydrogen peroxide in the presence of a molybdenum or inorganic molybdenum compound and a phosphate compound catalyst and distilling the resultant arsenic (V) compound to provide purified anhydrous hydrogen fluoride.
  • the process of this invention involves, generally, contacting feed hydrogen fluoride which may be industrial grade anhydrous hydrogen fluoride, or an intermediate product obtained in the manufacturing process, with an effective amount of an oxidizer and reacting the mixture under conditions suitable to oxidize the arsenic impurity to produce a very low arsenic hydrogen fluoride product stream and separating the product stream to produce a very low arsenic hydrogen fluoride product.
  • feed hydrogen fluoride which may be industrial grade anhydrous hydrogen fluoride, or an intermediate product obtained in the manufacturing process
  • oxidizer an amount effective to oxidize the arsenic impu ⁇ ty in the feed hydrogen fluo ⁇ de to produce very low arsenic hydrogen fluo ⁇ de
  • very iow arsenic hydrogen fluonde is meant anhydrous hydrogen fluo ⁇ de with arsenic levels of at least less than about 2 ppb or aqueous hydrogen fluoride with correspondingly low levels of arsenic It has been discovered that, with either multiple additions or a single sustained addition of oxidtzer, hydrogen fluoride with very low levels of arsenic may be obtained
  • feed hydrogen fluo ⁇ de which may be industrial grade anhydrous hydrogen fluo ⁇ de, or an intermediate obtained in the manufacture of anhydrous hydrogen fluo ⁇ de, and an oxidizer are fed into a reactor to produce a very low arsenic hydrogen fluo ⁇ de product stream
  • the product stream is fed into a distillation column in order to separate the resultant, very low arsenic hydrogen fluoride product from the waste
  • the waste stream may be further treated to recover volatile hydrogen fluo ⁇ de and the non-volatile arsenic impu ⁇ ty separated and recovered as a useful product or discarded, as disclosed in United States Patent Nos 5,089,241, 4,929,435 and 4,756,899 incorporated herein by reference
  • the process of this invention may be practiced in either batch or continuous mode, or a combination of these modes
  • the hydrogen fluo ⁇ de for use as feed hydrogen fluo ⁇ de in the process of this invention may be hydrogen fluonde that is an intermediate product obtained du ⁇ ng manufacture and is at least 95 % by weight hydrogen fluo ⁇ de
  • the hydrogen fluo ⁇ de feed mate ⁇ al used is high punty anhydrous hydrogen fluonde that is at least 99 9 % hydrogen fluo ⁇ de by weight
  • the amount of arsenic impu ⁇ ty will be about 10 to about 500 ppm
  • the arsenic tmpu ⁇ ty ofthe feed hydrogen fluo ⁇ de is from about 1 to about 100 ppm
  • the feed hydrogen fluo ⁇ de contains arsenic impurities above the preferred range, preferably the feed hydrogen fluo ⁇ de is first purified according to the process disclosed in US Patent No 4,929,435 which is incorporated by reference in its entirety herein and, subsequently, the process of this invention is employed
  • oxidizer a compound or compounds capable of oxidizing volatile arsenic (III) compounds to nonvolatile arsenic (V) compounds
  • oxidizers include, without limitation, potassium permanganate, fluorine, chlorine, persulfuric acid and salts thereof, sulfuric acid, chromic oxide, chromate salts, hydrogen peroxide, oxygen, ozone, and mixtures thereof with potassium fluoride, metal fluoride salts, hydrogen chloride or methanol
  • hydrogen peroxide is used
  • the hydrogen peroxide useful in the invention process may be either reagent grade that is a pure compound with very little added stabilizer or commercial grade that contains substantial quantities of stabilizers. Any commercially available strength of hydrogen peroxide may be used Preferably, 50% peroxide is used in order to limit the amount of water added to the process
  • a catalyst may be added either individually or in admixture with the peroxide.
  • the amount of peroxide used, as well as the nature and amount ofthe catalyst useful in the present invention are disclosed fully in US Patent No 4,929,435 Generally, from about 0.1 to about 1 5 weight percent peroxide is used based on 100% anhydrous hydrogen fluoride. Preferably, from about 0 1 to about 0 5 weight percent is used
  • Suitable catalysts for use in this invention comprise a molybdenum component or a vanadium component and a phosphate component
  • the molybdenum component may include, without limitation, molybdenum metal, an organic molybdenum compound such as molybdenum acetyl acetonate or an inorganic molybdenum compound such as a mono- or polyalkali metal molybdate, a molybdenum oxide, or a mono- or polyammonium molybdate
  • ammonium molybdate is used
  • the vanadium component may include, without limitation, vanadium metal, an organic vanadium compound such as vanadyl acetate, or an inorganic vanadium compound such as mono- or polyalkali metal vanadate, a vanadium oxide, or mono- or polyammonium vanadate
  • the preferred vanadium component is sodium meta-vanadate, sodium orthovanadate, and ammonium vanadate
  • Suitable phosphate components include, without limitation, phosphoric acid and inorganic phosphates such as mono- and polyalkali metal phosphates or polyphosphates and mono- and polyammonium phosphates or organic phosphonates used as stabilizers in peroxide
  • the preferred phosphate is sodium tripolyphosphate If commercial grade hydrogen peroxide is used containing phosphates or phosphate containing compounds, the need for the phosphate component ofthe catalyst may be eliminated
  • the amount of catalyst, including the proportions of components used, is that amount effective to achieve satisfactory rates at which the volatile arsenic (III) impurities ofthe hydrogen fluoride are converted to nonvolatile arsenic (V) compounds
  • the particular amount and proportions will vary depending on the particular components chosen and are readily ascertainable by one of ordinary skill in the art
  • the metal component is required and at least about 3 5 ppm of the phosphate component is required.
  • the other component preferably is present in at least 3 to 4 times the amount.
  • the preferred amount of the phosphate component is from about 25 to about 400 ppm, preferably from about 100 to about 400 ppm for phosphoric acid and from about 10 to about 55 for sodium tripolyphosphate.
  • anhydrous hydrogen fluoride with arsenic levels of at least less than about 2 ppb, or aqueous hydrogen fluoride with correspondingly low arsenic levels may be obtained using either multiple additions or a single sustained addition of oxidizer to the feed hydrogen fluoride.
  • single sustained addition is meant that the addition ofthe oxidizer occurs gradually over the total reaction time
  • the multiple additions or single sustained addition permits sufficient time for the peroxide - arsenic (III) reaction, which is an extremely rapid reaction due to the rapid decomposition of peroxide, to proceed in order to produce hydrogen fluoride with very low levels of arsenic impurity.
  • peroxide and catalyst may be added together to the feed hydrogen fluoride slowly in a single sustained addition.
  • the peroxide and catalyst may be added in stages in a batch process or in multiple stages in a continuous process. If multiple additions are used for any of the oxidizers, any number of additions may be made. Preferably and conveniently, at least two additions, more preferably four additions, are made.
  • the catalyst need not be added with each addition of peroxide so long as the total amount of catalyst used is at least 3 7 ppm of the metal component and at least 3 5 ppm of the phosphate component based on 100% hydrogen fluoride.
  • the catalyst is not added with each addition of peroxide because the addition of the catalyst adds water to the process. Also preferably, the catalyst is added before the peroxide to allow adequate mixing and performance of the catalytic function.
  • the product of this invention is very low arsenic hydrogen fluoride.
  • the reaction time for the process of this invention is that time effective to produce the very low arsenic hydrogen fluoride product stream
  • the total reaction time, generally, for either the single sustained addition or the multiple additions of the oxidizer is from about two minutes to about sixty minutes, preferably from about fifteen minutes to about sixty minutes.
  • the process of this invention may be carried out at a temperature from about 0° C to about 75° C, preferably from about 15° C to about 75° C More preferably, the reaction is carried out at from about 40° C to about 65° C.
  • Organic contaminants of as little as 100 ppm can decrease the efficiency of the oxidation reaction
  • an organic oxidant such as nitric acid or nitric acid salts may be added in an amount of from about 2 to about 10 ppm for each 100 ppm of organic contaminant The optimum amount is readily determinable by one ordinarily skilled in the art.
  • the point of addition of the oxidizing agent is not critical, but preferably is to the feed hydrogen fluoride stream prior to the addition of catalyst.
  • the process ofthe invention must be conducted in equipment that is not attacked by anhydrous hydrogen fluoride in order to preclude contamination by material from the reactor or equipment. Accordingly, surfaces ofthe reactor, distillation column, column packing, condenser, and receiver that contact the hydrogen fluoride must be inert to hydrogen fluoride. Suitable inert materials include, without limitation, low carbon steel, stainless steel, nickel, nickel alloys, platinum, polyethylene, polyvinyl chloride, and fluorocarbon polymers. Preferably, fluorocarbon polymers are used if avoidance of metal impurities is desirable or the hydrogen fluoride will be diluted with water to make an aqueous product.
  • any known method including distillation at atmospheric pressure, may be used to separate the nonvolatile arsenic impurities to produce very low arsenic hydrogen fluoride product
  • Example 1 As a control, 200 g AHF were introduced into a jacketed circulation reactor cooled with ice water and the reactor and contents warmed to 55° C with hot water Stabilized 50% hydrogen peroxide and aqueous reagent grade ammonium molybdate and aqueous sodium tripolyphosphate catalysts were then added as a mixture An increase in pressure and temperature were observed The reaction ran for about 30 minutes and the reactor was then cooled with ice water The mixture in the reactor was sampled and analyzed for arsenic (III) It is known that arsenic (III) will be distnaded evenly in the vapor and liquid phases and, thus, no distillation was attempted The reaction mixture was diluted to 50% HF for analysis and the results on a 100% HF basis are listed on Table 1.
  • Example 2 The procedure and equipment of Example 1 were modified in that two additions of hydrogen peroxide and catalyst mixtures were used Additionally, during reactor cool down, a packed reflux column, reflux splitter and distillation column were attached. The reactor was vented through the reflux and distillation columns to avoid loss of AHF and to remove inert and other low boiling substances such as phosphorous pentafluoride, phosphorous trifluoride, nitrogen and chlorine containing compounds, silicon tetrafluoride and oxygen from the peroxide composition. Heat was applied to the reactor and, at steady state, the reflux started and total reflux maintained for 1 hr For purposes of atmospheric single distillation ("D- l"), the sample was collected in a PFA bottle packed in dry ice to collect the AHF. The collected AHF was diluted to 50% HF for analysis and the results on a 100% HF basis are listed on Table 1
  • D- l atmospheric single distillation
  • Example 3 400 g AHF were introduced into a jacketed reactor cooled with ice water and the reactor and contents warmed to about 55° C with hot water. Stabilized 50%) hydrogen peroxide was mixed with aqueous ammonium molybdate and sodium tripolyphosphate catalysts and added to the reactor The reaction ran for 15 minutes. A second addition of the peroxide and catalyst was performed. After 15 minutes, peroxide alone was added and allowed to react for 15 minutes. A fourth addition of peroxide alone was allowed to react for 15 minutes. The reactor was cooled with ice water and the reaction mixture distilled and analyzed as in Example 2.
  • Example 4 and 5 For Examples 4 and 5, the procedure for Example 3 was followed except that a second atmospheric distillation ("D-2") was performed. The D-1 distilled AHF was sampled and then reintroduced into the clean reactor and distilled under the same conditions as for D-1. The distilled samples were analyzed as in Example 2 and the results on a 100% HF basis are listed on Table 1.
  • D-2 second atmospheric distillation
  • Example 1 demonstrates that, although low levels of arsenic impurity can be achieved with the prior art method, very low levels cannot be attained.
  • Examples 3 through 5 illustrate that very low levels of arsenic can be attained by multiple additions of hydrogen peroxide and catalysts.
  • Prospective Examples 1 - 5 The use ofthe oxidizers potassium permanganate, chromic oxide, chromate salts, persulfuric acid and persulfate are demonstrated in Prospective Examples 1 through 5, respectively, as follows For each of the Prospective Examples 1 through 5, 400g anhydrous HF are introduced into a jacketed circulation reactor cooled with ice water and the reactor contents are warmed to about 25° C with hot water.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

L'invention se rapporte à un procédé de préparation de fluorure d'hydrogène à très faible teneur en arsenic. L'invention se rapporte plus spécifiquement à un procédé dans lequel le fluorure d'hydrogène anhydre de qualité industrielle, ou un produit intermédiaire obtenu au cours du processus de production du fluorure d'hydrogène, est mis en contact avec un agent d'oxydation afin d'oxyder les impuretés d'arsenic et d'obtenir un fluorure d'hydrogène anhydre dont le taux d'arsenic est au moins inférieur à deux parts par milliard, ou un fluorure d'hydrogène aqueux dont le taux d'arsenic est proportionnellement faible.
EP96938820A 1995-11-13 1996-11-08 Production de fluorure d'hydrogene a tres faible teneur en arsenic Withdrawn EP0879211A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US55565995A 1995-11-13 1995-11-13
US555659 1995-11-13
PCT/US1996/017924 WO1997018158A1 (fr) 1995-11-13 1996-11-08 Production de fluorure d'hydrogene a tres faible teneur en arsenic

Publications (1)

Publication Number Publication Date
EP0879211A1 true EP0879211A1 (fr) 1998-11-25

Family

ID=24218128

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96938820A Withdrawn EP0879211A1 (fr) 1995-11-13 1996-11-08 Production de fluorure d'hydrogene a tres faible teneur en arsenic

Country Status (3)

Country Link
EP (1) EP0879211A1 (fr)
AU (1) AU7610796A (fr)
WO (1) WO1997018158A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115535965A (zh) * 2022-10-13 2022-12-30 云南氟磷电子科技有限公司 一种氢氟酸连续除砷的方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4032621A (en) * 1975-11-24 1977-06-28 E. I. Du Pont De Nemours And Company Preparation of hydrogen fluoride with low levels of arsenic, iron and sulfite
US4929435A (en) * 1987-02-12 1990-05-29 Allied-Signal Inc. Manufacture of high purity low arsenic anhydrous hydrogen fluoride
US4756899A (en) * 1987-02-12 1988-07-12 Allied-Signal Inc. Manufacture of high purity low arsenic anhydrous hydrogen fluoride

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9718158A1 *

Also Published As

Publication number Publication date
AU7610796A (en) 1997-06-05
MX9803559A (es) 1998-09-30
WO1997018158A1 (fr) 1997-05-22

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