WO2004076353A1 - Procede de preparation de fluorure de calcium - Google Patents

Procede de preparation de fluorure de calcium Download PDF

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Publication number
WO2004076353A1
WO2004076353A1 PCT/EP2004/002035 EP2004002035W WO2004076353A1 WO 2004076353 A1 WO2004076353 A1 WO 2004076353A1 EP 2004002035 W EP2004002035 W EP 2004002035W WO 2004076353 A1 WO2004076353 A1 WO 2004076353A1
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WO
WIPO (PCT)
Prior art keywords
fluoride
calcium
aqueous solution
calcium fluoride
acid
Prior art date
Application number
PCT/EP2004/002035
Other languages
English (en)
Inventor
Thomas Scholten
Harald Heuduk
Michael Theissen
Original Assignee
Honeywell Specialty Chemicals Seelze Gmbh
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
Priority claimed from DE2003109611 external-priority patent/DE10309611A1/de
Application filed by Honeywell Specialty Chemicals Seelze Gmbh filed Critical Honeywell Specialty Chemicals Seelze Gmbh
Publication of WO2004076353A1 publication Critical patent/WO2004076353A1/fr

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/02—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of crystals, e.g. rock-salt, semi-conductors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/20—Halides
    • C01F11/22—Fluorides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/10—Solid density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/20—Powder free flowing behaviour
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Definitions

  • the present invention relates to a process for preparing calcium fluoride wherein an aqueous solution of at least one calcium salt and an aqueous solution containing fluoride ions are added to a solution of an acid which is free of fluoride.
  • high purity calcium fluoride is prepared in the process according to the invention, which is different from known calcium fluoride.
  • the present invention also relates to the calcium fluoride obtainable by the process according to the invention and to the use of the calcium fluoride for producing single crystals, in particular for litographic processes.
  • the invention relates to optical items, especially to lenses, mirrors and optical items having plane surfaces, such as prisms or cubes consisting primarily of the calcium fluoride according to the present invention.
  • calcium fluoride is normally produced by the so-called carbonate process.
  • this process has the disadvantage that the calcium carbonate which is not dissolved in the aqueous systems often used does not react completely when reacted with e.g. hydrogen fluoride, and that the final product includes carbonate as impurity. Tempering the product may lead to the formation of calcium oxide which is an impurity as well. All impurities as well as the physical properties of calcium fluoride have a considerable impact on the y application such as microelectronic applications or litographic processes using optical items made from calcium fluoride.
  • the invention relates to a process for preparing calcium fluoride, comprising step (i):
  • the at least one acid which is free of fluoride is soluble in water.
  • the solution to which the solution of the at least one calcium salt and the solution containing fluoride ions are added is an aqueous solution of an acid which is soluble in water.
  • the selection of the at least one acid which is essentially free of fluoride there is no special limitation as to the selection of the at least one acid which is essentially free of fluoride.
  • hydrochloric acid, nitric acid, formic acid and acetic acid or a mixture of two or more thereof are preferably used.
  • the present invention relates to a process as described above characterized in that the acid which is essentially free of fluoride is preferably selected from the group consisting of hydrochloric acid, nitric acid, formic acid, acetic acid and a mixture of two or more thereof.
  • Acids are particularly preferred which, when used, allow the pH value of the solution in which the aqueous solution containing the dissolved calcium salt and fluoride ions are contacted to be adjusted to have a value of 1 or below.
  • the present invention also relates to a process as described above characterized in that the solution containing the at least one acid which is essentially free of fluo- ride is an aqueous solution having a pH value of 1 or below. If the aqueous solutions containing on the one hand the at least one calcium salt and on the other hand fluoride ions are brought together in the acidic solution, the pH value of the new resulting mixture may change. According to the inventive process it is possible in this case to regulate the pH value of the mixture so that it remains constant or that it is changed in a desirable way.
  • the pH value of the mixture can be regulated in such a way that it is in a range of 1 or below thereby remaining constant or varying, independent of the addition of the aqueous solutions containing the at least one calcium salt on the one hand and fluoride ions on the other. Controlling and regulating the pH value can be achieved by methods known in the art.
  • the pH value of the acidic solution is adjusted prior to the addition of the other aqueous solutions so that it remains in the desired range even without regulation after the addition of said solutions.
  • the at least one calcium salt which is dissolved in one of the aqueous solutions is used.
  • calcium salts of the present invention calcium chloride, calcium nitrate, calcium formate, calcium acetate or a mixture of two or more thereof is used.
  • the present invention also relates to a process as described above character- ized in that the at least one calcium salt is selected from the group consisting of calcium chloride, calcium nitrate, calcium formate, calcium acetate and a mixture of two or more thereof.
  • solu- tion are preferred which contain hydrogen fluoride dissolved in water or ammonium fluoride dissolved in water or hydrogen fluoride as well as ammonium fluoride.
  • the present invention also relates to a process as described above characterized in that the at least one aqueous solution containing fluoride ions is an aqueous so- lution of hydrogen fluoride, ammonium fluoride or a mixture thereof.
  • aqueous solutions are: aqueous solution containing calcium chloride, aqueous solution containing hydrogen fluoride, aqueous solution containing hydrogen chloride; aqueous solution containing calcium nitrate, aqueous solution containing hydrogen fluoride, aqueous solution containing nitric acid; - aqueous solution containing calcium acetate, aqueous solution containing hydrogen fluoride, aqueous solution containing hydrogen chloride.
  • the aqueous solutions may be added to the acidic solution in arbitrary order.
  • One possibility e.g., is to add the solution of the calcium salt to the acidic solution first and then to add the solution containing fluoride ions to the resulting mixture.
  • Another possibility e.g., is to add the solution containing fluoride ions to the acidic solution first and then to add the solution of the calcium salt to the resulting mixture. If two or more solutions containing fluoride ions or two or more solutions containing calcium salt or two or more solutions containing fluoride ions as well as two or more solutions con- taining calcium salt are used, all possibilities with respect to the order of adding the respective solutions may be used.
  • the solution containing the at least one calcium salt and the solution containing fluoride ions are added to the acidic solution synchronously.
  • synchronous addition defines processes in which dependent on the concentration of the at least one solution containing the at least one calcium salt and the concentration of the at least one solution containing fluoride ions are added to the acidic solution in such a way that calcium ions and fluoride ions are added to the acidic solution with a stoichiometric ratio of essentially 1 : 2.
  • the present invention also relates to a process as described above wherein the at least one aqueous solution of the at least one calcium salt and the at least one aqueous solution containing fluoride ions are added synchronously to the at least one solution containing an acid which is essentially free of fluoride.
  • a certain amount of hydrogen fluoride and / or ammonium fluoride is added to the preferably aqueous, acidic solution prior to the synchronous addition of the aqueous solutions in order to avoid a surplus of calcium ions.
  • the amount of said added hydrogen fluoride and / or ammonium fluoride and the amount may be adjusted to the amounts of calcium ions and fluoride ions which are synchronously added to the acidic solutions per time unit.
  • the synchronous addition can be achieved by all possible processes.
  • the concentrations of the aqueous solutions added to the acidic solution and the addition rate of said solutions may be coordinated in such a way that the desired amount of calcium ions and fluoride ions are brought together per time unit in the acidic solution.
  • the concentrations of the aqueous solutions may and the addition rate may be adjusted to the experimental volume restrictions of the reactor.
  • concentrated solutions of calcium salt and fluoride ions or solutions with a calcium salt or fluoride ion content of 60 wt-%, 40 w -% or less can be brought together.
  • the concentrations of the different aqueous solutions which are brought together can be different from each other. Diluted solutions are generally preferred because of the precision of measuring out the exact doses.
  • the addition of the aqueous solutions can be carried out continuously or in discrete steps (partial charges).
  • calcium ions and fluoride ions are added in a stoichiometric ratio of essentially 1 : 2 per time unit to the acidic solution.
  • calcium ions and fluoride ions are added in a stoichiometric ratio of essentially 1 : 2 essentially at the same time in each addition step to the acidic solution.
  • the addition [of the aqueous solution] can be carried out continuously or in discrete, particularly small steps, preferably synchronously.
  • concentration of the calcium salt containing aqueous solution with respect to calcium salt generally is in the range of from 5 to 55wt.-%, preferably of from 20 to 45 wt.-% and especially preferably of from 30 to 40 wt-%.
  • the concentration of the fluoride ions containing aqueous solution with respect to fluoride ions generally is in the range of from 5 to 65 wt-%, preferably of from 10 to 60 wt- % and especially preferably of from 20 to 50 wt-%.
  • While adding the aqueous solutions to the acidic solution the resulting mixture in which the calcium fluoride is formed is kept homogeneous by one or more methods wherein one only has to take into account that keeping the mixture homogeneous does not prevent the calcium fluoride from being formed.
  • a preferred method is stirring the mixture, and stirring can be carried out by every suitable method.
  • the aqueous solutions are added to the acidic solution at temperatures above room temperature. More preferably the addition takes place at temperatures of from 50 to 135 °C, more preferably of from 60 to 130 °C, and most preferably of from 80 to 125 °C.
  • the present invention also relates to a process as described above wherein the at least one aqueous solution of the at least one calcium salt and the at least one aqueous solution containing fluoride ions are added to the at least one solution containing an acid which is essentially free of fluoride at temperatures of from 80 to 125 °C.
  • the temperatures of the solutions to be added and the acidic solution may be chosen prior to the addition or the additions in such a way that the temperature of the mixture resulting from the addition is within the preferred ranges described above.
  • the temperatures of the solutions to be added may be different from the preferred temperature ranges described above or may be within these ranges.
  • the tem- perature of the mixture resulting from the addition can be kept constant or may vary, e.g. in the preferred temperature ranges described above, during addition of the solutions by methods known in the art.
  • step (i) of the inventive process is isolated from the mixture, preferably after stopping the addition of the aqueous solutions.
  • a batch process or- a continuous process can be used, e. g. in a cascade mixer, a batch reactor with continuous discharge or a reaction tube.
  • a first cooling step may take place in a first vessel like, e.g., the reaction vessel the calcium fluoride is formed in, and in a second cooling step the whole reaction mixture or a part of it may be cooled down in a second vessel. It maybe desirable to subject the solution containing the calcium fluoride to the separation step for obtaining calcium fluoride without cooling down significantly.
  • the calcium fluoride formed is separated from the reaction solution by methods known in the art like, e.g., decanting washing, extraction by suction, filtration or a combination of two or more of these methods wherein the same or different methods may be carried out several times one after the other. It is especially preferred to wash the product several times with water.
  • the isolated product is then subjected to a thermal treatment in a further step.
  • the present invention also relates to a process as described above, additionally comprising steps (ii) and (iii): (ii) isolation of the calcium fluoride formed in (i);
  • the thermal treatment is carried out in at least two steps (a) and (b).
  • the washed product is subjected at least once to a drying treatment in a step (a). It is possible to dry the product according to (a) several times wherein the drying temperatures may be equal or different.
  • the drying temperatures for the product are in arrange up to 200 °C.
  • the drying periods and temperatures may be adjusted to the moisture content of the product to be dried.
  • the dried product is subjected to at least one fur- ther thermal treatment in a step (b) wherein the temperature the dried product is subjected to is preferably higher than the drying temperature(s).
  • the temperature for this thermal treatment is in the range of 700 °C or below.
  • the present invention also relates to a process as described above character- ized in that according to (iii) the isolated product is subjected to at least one drying step (a), followed by at least one further thermal treatment in a step (b) wherein the temperature with regard to (b) is higher than the temperature(s) with regard to (a) and are in the range of 700 °C or below.
  • the thermal treatment according to (b) is carried out at a temperature of from 400 to 700 °C, more preferably of from 450 to 700 °C and even more preferably of from 500 to 700 °C.
  • the present invention also relates to a process as described above character- ized in that the thermal treatment (iii) comprises at least one step (b) in which the calcium fluoride is subjected to temperatures of from 500 to 700 °C.
  • the present invention relates to the calcium fluoride as such, which is obtainable by the process described above.
  • the present invention relates to calcium fluoride, obtainable by a process as described above wherein the calcium fluoride formed in the acidic solution is isolated according to (ii) and ther- mally treated according to (iii).
  • the inventive process is used to produce high purity calcium fluoride, which is novel as such and represents a further subject of the invention.
  • the term Huaweihigh purity as used in the context of the present application indi- cates that the degree of purity with respect to a certain kind of impurity of a solution, a suspension, a chemical compound such as a salt, a gas or a liquid is in the range of 250 ppm or below, preferably of 150 ppm or below, more preferably of 1 ppm or below, preferably of 100 ppb or below, more preferably of 10 ppb or below and especially preferably of 1 ppb or below.
  • a salt for in- stance, is defined as a high purity salt if it has a degree of purity x with respect to an impurity (X) and a degree of purity y with respect to another impurity (Y) wherein x is equal to or different from y, and x and y are within one of the above-mentioned ranges.
  • the calcium fluoride to be produced is a high-purity calcium fluoride it is generally advantageous to use starting materials introduced in the process according to (i) which are sufficiently pure.
  • Impurities of the calcium fluoride are for example metals like aluminum, antimony, arsenic, barium, beryllium, lead, cadmium, chromium, iron, gallium, germanium, gold, indium, potassium, cobalt, copper, lithium, magnesium, manganese, molybdenum, sodium, nickel, platinum, silver, silicon, strontium, thallium, titanium, vanadium, bismuth, zinc, tin or zirconium.
  • Other impurities are halogens such as chloride, bromide or iodide and, e.g. in the tempered product, oxygen.
  • the new calcium fluoride, according to the invention is characterized by the following maximum content of the relevant elements:
  • AAS Atomic absorption spectroscopy
  • ICP Inductively coupled plasma
  • the calcium product according to the invention can be distinguished by its crystalline free- flowing character with a high bulk density and - due to its crystallinity - a homogenous closed particle distribution. (The particle distribution is measured by using a Horiba Granulometer LA 920).
  • PE polyethylene
  • PP polypropylene
  • PVDF polyvinylidene fluoride
  • ETFE co-polymer of ethylene and tetrafluoro ethylene
  • PFA co-polymer of perfluoro ethylene and alkyl ether
  • PTFE polytetrafluoro ethylene
  • FEP fluorinated co-polymer of ethylene and propylene
  • Fluoroplastic materials such as PVDF, PTFE or PFA are preferred.
  • the resulting calcium fluoride has a packed weight of greater than or equal to 1.20 g/ml or above, preferably of greater than or equal to 1.30 g/ml and especially preferably of greater than or equal to 1.40 g/ml or above.
  • the packed weight is determined by caring out a graduated cylinder which is arbitrarily filled with (a) substance and weighed.
  • the present invention also relates to calcium fluoride as described above, having a packed weight of greater than or equal to 1.20 g/ml or above, preferably of greater than or equal to 1.30 g/ml and especially preferably of greater than or equal to 1.40 g/ml or above.
  • the present invention also describes a process as described above wherein the calcium fluoride resulting from step (iii) has a packed weight as described above.
  • the calcium fluoride prepared according to the invention may be used in all possible fields in which calcium fluoride is used.
  • litographic applications are a preferred field of usage.
  • litographic tech- niques are used to produce semiconductor wafers.
  • UV radiation with wavelengths below 200 nm which is generated by an excimer laser based on noble gas-halogene or by a halogene laser based on F 2 .
  • the optical lenses used therein must have a high transparency for the UV radiation.
  • Usable raw materials for the lenses are fluorides and espe- cially calcium fluoride. Generally the material is used as a single crystal or as layers in which the calcium ions and fluoride ions are present without bad spots.
  • the calcium fluoride In order to comply with the necessary specifications the calcium fluoride must have high purity quality and, e.g., an extremely low content of oxygen and metals.
  • the present applications also relates to the use of calcium fluoride, obtainable by a process as described above or of calcium fluoride as such, as described above, for producing single crystals.
  • the present invention also relates to the use as described above for producing optical items, particularly lenses, mirrors and optical items having plane boundaries, such as prisms and cubes consisting primarily of the calcium fluoride according to the present invention, especially for the use in litographic processes.
  • optical items, particularly lenses, mirrors and optical items having plane boundaries, such as prisms and cubes consisting primarily of the calcium fluoride according to the present invention are further subject of the invention.
  • the equipment used was a reaction vessel consisting of a cooler and a stirring device with a stirrer motor.
  • the system is closed with exception of the cooler, and all parts contacting the product and internal parts are made of PFA or Teflon.
  • the product was dried at 120 °C overnight, followed by tempering. During tempering the product was heated for 4 hrs. at temperatures up to 650 °C. The product was obtained as a white crystalline solid having a packed weight of 1.42 g/ml. The oxygen content was less or equal to 30 ppm.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

L'invention concerne un procédé de préparation de fluorure de calcium comprenant l'étape suivante (i) qui consiste : à ajouter au moins une solution aqueuse de sel de calcium et au moins une solution aqueuse contenant des ions fluorure à une solution contenant un acide de préférence sensiblement dépourvu de fluorure, ce qui permet d'obtenir du fluorure de calcium.
PCT/EP2004/002035 2003-02-28 2004-03-01 Procede de preparation de fluorure de calcium WO2004076353A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE10309611.6 2003-02-28
DE2003109611 DE10309611A1 (de) 2003-02-28 2003-02-28 Verfahren zur Herstellung von Calciumfluorid
US50657803P 2003-09-24 2003-09-24
US60/506,578 2003-09-24

Publications (1)

Publication Number Publication Date
WO2004076353A1 true WO2004076353A1 (fr) 2004-09-10

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PCT/EP2004/002035 WO2004076353A1 (fr) 2003-02-28 2004-03-01 Procede de preparation de fluorure de calcium

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006079417A1 (fr) 2005-01-27 2006-08-03 Unilever N.V. Dispositif et procede d'adoucissement d'eau
CN110282647A (zh) * 2019-08-02 2019-09-27 辽宁星空新能源发展有限公司 一种快速沉淀制备多孔氟化钙立方体的方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2653857A (en) * 1951-05-01 1953-09-29 Gen Electric Preparation of calcium fluoride
RO88593A2 (fr) * 1984-02-03 1986-03-31 Institutul Central De Fizica,Ro Procede pour la preparation du fluorure de calcium
EP0506050A1 (fr) * 1991-03-27 1992-09-30 QVF Glastechnik GmbH Procédé de préparation d'acide chlorhydrique purifiée d'halogènes étrangers
US20010008540A1 (en) * 1996-03-22 2001-07-19 Tomoru Oba Calcium flouride crystal, optical article and exposure apparatus for photo-lithography using the same
US20030000456A1 (en) * 1999-10-05 2003-01-02 Mayolet Alexandre M. Beads of a polycrystalline alkali-metal or alkaline-earth metal fluoride, their preparation, and their use for preparing optical single crystals
WO2003008674A2 (fr) * 2001-07-20 2003-01-30 Corning Incorporated Procede de fabrication de cristaux optiques de fluorure de haute purete

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2653857A (en) * 1951-05-01 1953-09-29 Gen Electric Preparation of calcium fluoride
RO88593A2 (fr) * 1984-02-03 1986-03-31 Institutul Central De Fizica,Ro Procede pour la preparation du fluorure de calcium
EP0506050A1 (fr) * 1991-03-27 1992-09-30 QVF Glastechnik GmbH Procédé de préparation d'acide chlorhydrique purifiée d'halogènes étrangers
US20010008540A1 (en) * 1996-03-22 2001-07-19 Tomoru Oba Calcium flouride crystal, optical article and exposure apparatus for photo-lithography using the same
US20030000456A1 (en) * 1999-10-05 2003-01-02 Mayolet Alexandre M. Beads of a polycrystalline alkali-metal or alkaline-earth metal fluoride, their preparation, and their use for preparing optical single crystals
WO2003008674A2 (fr) * 2001-07-20 2003-01-30 Corning Incorporated Procede de fabrication de cristaux optiques de fluorure de haute purete

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 198639, Derwent World Patents Index; Class E33, AN 1986-256552, XP002280136 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006079417A1 (fr) 2005-01-27 2006-08-03 Unilever N.V. Dispositif et procede d'adoucissement d'eau
CN110282647A (zh) * 2019-08-02 2019-09-27 辽宁星空新能源发展有限公司 一种快速沉淀制备多孔氟化钙立方体的方法

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