CN1558869A - Method for producing nitrogen trifluoride - Google Patents

Method for producing nitrogen trifluoride Download PDF

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Publication number
CN1558869A
CN1558869A CNA028188608A CN02818860A CN1558869A CN 1558869 A CN1558869 A CN 1558869A CN A028188608 A CNA028188608 A CN A028188608A CN 02818860 A CN02818860 A CN 02818860A CN 1558869 A CN1558869 A CN 1558869A
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China
Prior art keywords
sorbing agent
nitrogen trifluoride
metal
naf
hydrogen fluoride
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Granted
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CNA028188608A
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Chinese (zh)
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CN1301899C (en
Inventor
S・A・扎伊策夫
S·A·扎伊策夫
库兹内特佐夫
A·S·库兹内特佐夫
利沃夫
V·A·利沃夫
门索夫
V·S·门索夫
拉比诺维奇
R·L·拉比诺维奇
萨波兹尼科夫
M·V·萨波兹尼科夫
塔尔金
V·S·塔尔金
绍彭
V·P·绍彭
巴拉巴诺夫
V·G·巴拉巴诺夫
维诺格拉多夫
D·V·维诺格拉多夫
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ZAO ASTOR ELECTRONICS
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ZAO ASTOR ELECTRONICS
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    • 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
    • C01B7/01—Chlorine; Hydrogen chloride
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/083—Compounds containing nitrogen and non-metals and optionally metals containing one or more halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/083—Compounds containing nitrogen and non-metals and optionally metals containing one or more halogen atoms
    • C01B21/0832—Binary compounds of nitrogen with halogens
    • C01B21/0835—Nitrogen trifluoride

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

The invention relates to inorganic chemistry, in particular to methods for producing nitrogen trifluoride. The inventive method consists in fluorating the solid phase of ammonium polyfluoride salt having the formula NH 4Fx HF, wherein x is higher than 0 to 1.3 and can be equal to 1.3. The initial salt is used mixed with a sorbing agent which is capable to sorb hydrogen fluoride formed by synthesis. Said sorbing agent is embodied in the form of metal fluorides having the formula MeF, wherein Me is a metal of the 1<st> group of the Periodic table, preferably NaF, KF and LiF. RbF and CsFF can be also used, but the use thereof being economically impractical. The production of nitrogen trifluoride is carried out at a temperature ranging from 20 to 125 DEG C. Said invention makes it possible to totally use the initial salt NH 4Fx HF and to remove hydrogen fluoride thus produced.

Description

The manufacture method of nitrogen trifluoride
The present invention relates to domain of inorganic chemistry, more particularly, relate to the manufacture method of nitrogen trifluoride.In chemical industry, use nitrogen trifluoride as fluorizating agent and fuel oxidizer.In electronic industry, use it in the dry etch process as not staying sedimental gas; It is used in CVD (Chemical Vapor Deposition) apparatus also is known.
Concerning the manufacturing of nitrogen trifluoride, mainly contain 3 currently known methodss:
1. electrolyzing fused fluoram [patent US 3235474, classification 204/63, open day 1961.10.2]
Under 130-160 ℃, 0.2-0.4MPa to the liquid-phase fluorination [patent US4091081, classification 23/406, an open day .1978.5.23] of fusion fluoram
3. fluoridizing solid-state ammonium and metal composite fluorochemical.The present invention relates to this method.
Mutual-through type is (NH 4) xMF y(NH 4) xMM 1F ySolid-state ammonium and the fluorizated method of metal composite fluorochemical be known: x=1-3 wherein, y=4-7, M=Fe, Al, Ti and other metal, M 1=Li, Na, K[patent, US 4543242, C01B21/83B, 1985.9.24].
This method can be carried out in a continuous manner, comprises the fluorine gas of supplying with rare gas element (nitrogen, argon gas) dilution.Use compound Neutral ammonium fluoride with solid form, thereby guarantee reaction stability with specified dimension.The reaction yield of calculating with fluorine is 80-85%.
The shortcoming of this method is that the cost of initial ammonium and metal composite fluorochemical is high and must handles the metal fluoride that forms in the method.
Classification number is C01B21/083 in JP3232710, and submitting day to is 1990.2.6, the open day technical scheme of representing the most recent prior art that discloses for 1991.10.16.Described according to present method, nitrogen trifluoride is to be that 2: 1 the fluorine and the mixture reaction of metal fluoride and ammonium salt obtain by weight ratio.This is reflected at and carries out under 50-450 ℃ and feed fluorine gas nitrogen dilution in the reactor.
In this method,, for example, can use the fluorochemical of K, Na, Cu, Ca, Zn, Al, Sn, Pb, Mn, Ni, Co, Fe and other metal for metal fluoride; Yet, use NaF, CaF 2, FeF 3The time obtain best result.
For the inorganic ammonium salt in this method, can use (NH 4) 2SO 4, (NH 4) 2CO 2, NH 4NO 2, NH 4F, NH 4Cl, NH 4Br, NH 4I and other inorganic ammonium salt.
The ratio of metal fluoride and inorganic ammonium salt can be selected arbitrarily; Yet, it is desirable to this and be reflected under the excessive situation of metal fluoride and carry out, so the weight ratio of metal fluoride and inorganic ammonium salt is about 2: 1.
Temperature of reaction can approach room temperature or be higher than room temperature.From the angle of speed of reaction, it is desirable to temperature of reaction above 50 ℃.For avoiding destroying the NF of formation 3, it is desirable to temperature and be no more than 450 ℃.Consider some factor of productions (speed of reaction, heat energy loss etc.), it is desirable to temperature of reaction is 100-200 ℃.
The shortcoming of this method is to be formed by the liquid many Neutral ammonium fluorides that caused that react to each other between ammonium salt and by product hydrogen fluoride.Forming liquid phase can cause reactor to block and quicken corrosion to processing unit.The high temperature of this method has promoted to cause the side reaction of nitrogen generation, thereby greatly reduces the productive rate of target product nitrogen trifluoride.
The object of the present invention is to provide and a kind ofly can utilize raw material salt NH fully 4F.xHF removes the method that the hydrogen fluoride that forms is also removed reaction heat simultaneously.
This can simplify the method that nitrogen trifluoride is made, and a kind of manufacture method efficiently is provided, and is convenient to the processing of process byproducts greatly.
Above-mentioned purpose is NH by mutual-through type 4The fluoridizing of solid phase acid polyfluoro ammonium salt of F.xHF realize, wherein x is greater than 0 but be no more than 1.3 and can equal 1.3.When with can be adsorbed on the hydrofluoric sorbing agent that produces in the building-up process when mixing, use this initial salt.This sorbing agent is that the metal fluoride of MeF is formed by molecular formula, and wherein Me is the metal that is selected from periodic table of elements first family, is preferably NaF, KF, LiF, also available RbF and CsF; Yet they are unfavorable from economic angle.Make the method for nitrogen trifluoride and under 20-125 ℃, carry out sorbing agent: NH 4The weight ratio of F.xHF is 2-100.
" x " value in solid-state polyfluoro ammonium salt can be greater than 0 smaller or equal to 1.3.
When fluoridizing general formula is NH 4During the solid compounds of F.xHF, 1 mole of goal response product of every formation NF 3Will form the HF of (4+x) mole.
The hydrogen fluoride that forms by metal fluoride (being preferably the fluorochemical that is selected from periodic table of elements first family metal, for example LiF, NaF, KF) thus absorption forms many hydrofluorides of respective metal.Use a kind of special metal fluoride to carry out this adsorption process until hydrogen fluoride: the mol ratio of metal fluoride falls in 1: 1 to 1: 100 the scope.In order to remove moisture and volatile impunty, before metal fluoride is being fed reactor, by being heated to about 350 ℃ and with its activation.
Can powder, sheet or particulate form use this metal fluoride.Their size is unimportant for reactivity worth.
These metal fluorides can repeat the circulation of hydrogen fluoride absorption-desorption.For desorb, saturated sorbing agent is put into desorption device and its temperature progressively is elevated to 350 ℃ with the speed of 25-100 ℃/h.It is unfavorable heating up from the angle of technology very slowly, though temperature increase can cause the damage of sheet or grain pattern rapidly.The hydrogen fluoride that is obtained by desorb can be in application in fluorine chemical synthetic.
Both available some rare gas element of fluorine (for example, nitrogen, argon gas or the helium) dilution that feeds reaction zone can not diluted yet.
Implement this method in the accompanying drawings in the equipment of Xian Shiing.
This equipment is made up of mixing tank 1, reactor 2, phase splitter 3 and desorption device 4.
Mixing tank 1 has been filled initial salt NH 4The F.xHF and the fluorochemical of activated first family metal in advance, wherein x greater than 0 but be no more than 1.3 and x can equal 1.3., and they are transported to the reactor 2 from mixing tank obtaining uniform material with these reagent of specific mixed, this reactor diameter is 40mm, and length is 500mm, is made by nickel.
Fluorine or fluorine/noble gas mixtures are transported in the same reactor.Under 20-125 ℃, in reactor, fluoridize.Reaction mixture is transported in the phase splitter 3 by this reactor, and there, gaseous product separates with solid product.In the receptor (not shown), collect this gaseous product, therefrom this gaseous product is delivered to separation phase, isolate target product there.
With solid product, mainly be the metal fluoride that has adsorbed HF, be transported in the desorption device 4, there, they stand desorb and/or activation under 350 ℃.The hydrogen fluoride condensation that discharges is also collected with a receptor (not shown), and metal fluoride is circulated to mix stages.
This method form can be intermittent also can be successive.Following embodiment illustrates the present invention rather than limits its scope.
By the embodiment that lists in the table the present invention is described.
Embodiment 1. mixing tanks 1 have been filled 70g NH 4F.xHF and 700gNaF, wherein x=0.01.In desorption device 4, activate fresh Sodium Fluoride in advance, with 25 ℃ of/hour its temperature that raise.After temperature reaches 350 ℃, make Sodium Fluoride under this temperature, be incubated 5 hours.With described ratio is NaF: NH 4The reagent of F.xHF=10 is transported in the mixing tank and mixes to form uniform material.The solid reagent particulate is of a size of about 200 μ m.
Speed with 385g/h is transported to this solid reactants in the reactor 2 by mixing tank, and carries fluorine with the speed of 110g/h.The temperature of reactor is remained on 80 ℃.The reaction mixture of preparation is fed in the phase splitter 3 by reactor, and gaseous product separates with solid product there.Make the trap (in accompanying drawing not shown) of this gaseous product, and in receptor, collect this gaseous product by being used for collecting sour impurity.
The stratographic analysis of this gaseous product shows, they composed as follows, volume %:NF 3-87%, N 2-11.0%, other product (CF 4, N 2F 2, N 2F 4)-2.0%.
Will be by NH 4The solid phase that F.xHF forms, wherein x is transported to the HF desorption phase of carrying out smaller or equal to 1 under 350 ℃.Desorption time is 30h.After the desorb, NaF is cooled to 20-60 ℃ and be transported in the mixing tank 1.
Condensation hydrogen fluoride and be delivered to neutralizing treatment in the trap (not shown in the accompanying drawing).
In all other embodiment (2-11), all activate and desorb by embodiment 1.
The result who has shown other embodiment in the table.
Under the condition of suggestion, implement this method and can make full use of initial salt (many Neutral ammonium fluorides) and reasonably remove hydrogen fluoride, remove reaction heat simultaneously.
The embodiment of table experiment
Embodiment number The composition of solid-phase mixture ??MeF∶ ??NH 4The weight ratio of F.xHF Feeding rate, Grams Per Hour Temperature in the reactor, ℃ The composition volume % of gas phase NF 3Weight %
???????NH 4F.xHF The MeF value, gram Solid phase Fluorine or mixture ????N 2 ????NF 3 Other impurity ∑
The X value The gram number
????1 ????0.01 ??70 ?NaF-700 ??10.0 ??385 ????110.0 ????80 ????11.0 ????87.0 ????2.0 ????93.9
????2 ????1.0 ??82 ?NaF-620 ??7.6 ??350 ????75.0 ????40 ????21.1 ????77.2 ????1.7 ????89.5
????3 ????1.0 ??82 ?NaF-620 ??7.6 ??350 ????75.0 ????80 ????20.0 ????78.1 ????1.9 ????90.1
????4 ????1.0 ??82 ?NaF-620 ??7.6 ??350 ????75.0 ????125 ????22.0 ????76.2 ????1.8 ????87.3
????5 ????1.0 ??160 ?NaF-640 ??4.0 ??400 ????150.0 ????80 ????20.0 ????78.0 ????2.0 ????90.1
????6 ????0.01 ??70 ?NaF-400 ??5.7 ??235 ????105.0 ????80 ????19.0 ????79.2 ????1.8 ????91.5
????7 ????0.5 ??60 ?NaF-900 ??15.0 ??480 ????68.0 ????60 ????20.5 ????77.7 ????1.8 ????89.8
????8 ????0.01 ??7.0 ?NaF-700 ??100.0 ??350 ????10.5 ????20 ????19.8 ????79.0 ????1.2 ????90.8
????9 1 ????0.01 ??7.0 ?NaF-700 ??100.0 ??350 ????21.0 ????20 ????19.9 ????79.0 ????1.1 ????90.8
????10 ????1.0 ??70 ?LiF-140 ??2.0 ??105 ????65 ????60 ????21.0 ????78.0 ????1.0 ????90.5
????11 ????1.0 ??70 ?KF700 ??10.0 ??385 ????65 ????80 ????20.8 ????78.0 ????1.2 ????90.4
????12 2 ????1.0 ??70 NaF+LiF+KF 200+200+200 is 600g altogether 2 ??8.6 ??335 ????65 ????80 ????20.0 ????78.1 ????1.9 ????90.1
1In " fluorine or mixture " row of embodiment 9, be 10.5+10.5g fluorine and nitrogen mixture; In " composition of gas phase " row, do not calculate the nitrogen that injects.
2The geometric ratio mixture of fluorochemical NaF, LiF and KF

Claims (5)

1. the method by fluorinated solid ammonium salt manufacturing nitrogen trifluoride is characterized in that to molecular formula be NH 4The acid salt of many Neutral ammonium fluorides of F.xHF is fluoridized, and wherein x is greater than 0 but be no more than 1.3, under temperature 20-125 ℃, carries out this method being useful in the presence of the hydrofluoric sorbing agent of absorption, makes sorbing agent: NH 4The weight ratio of F.xHF remains in the scope of 2-100.
2. the method for claim 1, it is characterized in that using molecular formula as the compound of MeF or its mixture as sorbing agent, wherein Me is the metal that is selected from the periodic table of elements the 1st family.
3. claim 1 or 2 method is characterized in that preferably using NaF, LiF, KF or their mixture as sorbing agent.
4. arbitrary method among the claim 1-4 is characterized in that being up under 350 ℃ the temperature from the sorbing agent this sorbing agent of circulation behind the desorb hydrogen fluoride.
5. arbitrary method among the claim 1-5 is characterized in that before being transported to sorbing agent in the reactor, was up to 350 ℃ and with its activation by heating progressively.
CNB028188608A 2001-09-28 2002-05-20 Method for producing nitrogen trifluoride Expired - Fee Related CN1301899C (en)

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RU2001126320/12A RU2182556C1 (en) 2001-09-28 2001-09-28 Method of obtaining nitrogen trifluoride
RU2001126320 2001-09-28

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CN1301899C CN1301899C (en) 2007-02-28

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100460745C (en) * 2005-06-14 2009-02-11 株式会社厚成 Method of storing nitrogen trifluoride

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6071503A (en) * 1983-09-27 1985-04-23 Central Glass Co Ltd Manufacture of nf3
JP2930351B2 (en) * 1990-02-06 1999-08-03 関東電化工業株式会社 Manufacturing method of NF (3)
JP3727797B2 (en) * 1998-05-22 2005-12-14 セントラル硝子株式会社 Method for producing nitrogen trifluoride

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100460745C (en) * 2005-06-14 2009-02-11 株式会社厚成 Method of storing nitrogen trifluoride

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WO2003027010A1 (en) 2003-04-03
CN1301899C (en) 2007-02-28
KR20040054695A (en) 2004-06-25

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