DE10203914C1 - Recovery of hydrogen chloride, used directly as raw material e.g. in chlorosilane production, involves cooling waste gas from organosilane ester production from chlorosilane and alcohol and/or glycol without condensing hydrogen chloride - Google Patents
Recovery of hydrogen chloride, used directly as raw material e.g. in chlorosilane production, involves cooling waste gas from organosilane ester production from chlorosilane and alcohol and/or glycol without condensing hydrogen chlorideInfo
- Publication number
- DE10203914C1 DE10203914C1 DE2002103914 DE10203914A DE10203914C1 DE 10203914 C1 DE10203914 C1 DE 10203914C1 DE 2002103914 DE2002103914 DE 2002103914 DE 10203914 A DE10203914 A DE 10203914A DE 10203914 C1 DE10203914 C1 DE 10203914C1
- Authority
- DE
- Germany
- Prior art keywords
- hydrogen chloride
- chlorosilane
- production
- exhaust gas
- alcohol
- 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.)
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Links
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910000041 hydrogen chloride Inorganic materials 0.000 title claims abstract description 56
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 title claims abstract description 56
- -1 organosilane ester Chemical class 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 14
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000005046 Chlorosilane Substances 0.000 title claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 239000002912 waste gas Substances 0.000 title abstract description 8
- 238000001816 cooling Methods 0.000 title description 3
- 238000011084 recovery Methods 0.000 title description 3
- 239000002994 raw material Substances 0.000 title description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 4
- 125000004803 chlorobenzyl group Chemical group 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 150000001367 organochlorosilanes Chemical class 0.000 claims description 11
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 11
- 239000005052 trichlorosilane Substances 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 4
- 230000032050 esterification Effects 0.000 claims description 4
- HNEGJTWNOOWEMH-UHFFFAOYSA-N 1-fluoropropane Chemical group [CH2]CCF HNEGJTWNOOWEMH-UHFFFAOYSA-N 0.000 claims description 3
- 125000005999 2-bromoethyl group Chemical group 0.000 claims description 3
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 claims description 3
- 125000004777 2-fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 claims description 3
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 3
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 125000001153 fluoro group Chemical group F* 0.000 abstract 1
- 229920005555 halobutyl Polymers 0.000 abstract 1
- 125000005843 halogen group Chemical group 0.000 abstract 1
- 238000007038 hydrochlorination reaction Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- AAELHWDCDSZXGG-UHFFFAOYSA-L [Na+].[Cl+].[Cl-].[Cl-] Chemical compound [Na+].[Cl+].[Cl-].[Cl-] AAELHWDCDSZXGG-UHFFFAOYSA-L 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/002—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/204—Inorganic halogen compounds
- B01D2257/2045—Hydrochloric acid
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Silicon Compounds (AREA)
Abstract
Description
Die, vorliegende Erfindung betrifft die Herstellung von Chlorsilanen und Organosilanestern, insbesondere die Reinigung des bei der Organosilanesterherstellung anfallenden Chlorwasserstoff-haltigen Abgases und dessen Wiederverwertung.The present invention relates to the production of chlorosilanes and Organosilane esters, especially the cleaning of the Organosilane ester production of waste gas containing hydrogen chloride and its recycling.
Es ist bekannt, Organosilanester durch Umsetzung von Organochlorsilanen mit Alkoholen oder Glykolen unter gleichzeitiger Bildung von Chlorwasserstoff (HCl) zu erzeugen.It is known to use organosilane esters by reacting organochlorosilanes with Alcohols or glycols with simultaneous formation of hydrogen chloride (HCl) too produce.
Dabei wird der als Nebenprodukt entstehende Chlorwasserstoff in an sich bekannter Weise z. B. mit wässriger Natronlauge neutralisiert oder bei z. B. sehr tiefer Temperatur (tiefer -85°C bei Normaldruck) kondensiert und anschließend wieder zur Reinigung verdampft. Beide Verfahren weisen erhebliche Nachteile auf.The hydrogen chloride formed as a by-product is known per se Way z. B. neutralized with aqueous sodium hydroxide solution or at z. B. very deeper Temperature (lower -85 ° C at normal pressure) condensed and then back to Cleaning evaporates. Both methods have significant disadvantages.
So macht die Neutralisation von HCl mittels wässriger Natronlauge einen direkten Wiedereinsatz des bei der Organosilanestersynthese gebildeten Chlorwasserstoffs unmöglich. Hier muss beispielsweise erst durch einen aufwendigen Elektrolyseprozess aus dem Neutralisationsprodukt Natriumchlorid Chlor erzeugt und aus diesem durch Umsetzung mit Wasserstoff Chlorwasserstoff gewonnen werden.The neutralization of HCl by means of aqueous sodium hydroxide solution makes a direct one Reuse of the hydrogen chloride formed in organosilane ester synthesis impossible. Here, for example, must first be done by an elaborate Electrolysis process generated from the neutralization product sodium chloride chlorine and hydrogen chloride can be obtained from this by reaction with hydrogen.
Auch der Weg der Kondensation mit anschließender Verdampfung ist ein technisch und energetisch und damit auch finanziell sehr aufwendiger Weg, den Chlorwasserstoff wieder einzusetzen.The way of condensation with subsequent evaporation is also a technical one and energetically and therefore also financially very complex way Reuse hydrogen chloride.
Organochlorsilane werden im technischen Maßstab in der Regel durch Hydrosilylierung von ungesättigten organischen Verbindungen, z. B. Olefinen, ungesättigten organischen Aminen etc., mit Trichlorsilan in Gegenwart von geeigneten Katalysatoren hergestellt.Organochlorosilanes are usually produced on an industrial scale Hydrosilylation of unsaturated organic compounds, e.g. B. olefins, unsaturated organic amines etc., with trichlorosilane in the presence of suitable catalysts prepared.
Die Herstellung von Trichlorsilan kann durch Umsetzung von elementarem Silicium metall mit Chlorwasserstoff (Hydrochlorierung) bzw. durch Umsetzung mit Chlor (Chlorierung) erfolgen. Nach beiden Herstellvarianten werden Gemische aus im Wesentlichen Trichlorsilan und Tetrachlorsilan erhalten, die nach destillativer Reinigung in die reinen Komponenten Trichlorsilan und Tetrachlorsilan aufgetrennt werden können.The production of trichlorosilane can be done by reacting elemental silicon metal with hydrogen chloride (hydrochlorination) or by reaction with chlorine (Chlorination). According to both manufacturing variants, mixtures of in Mainly trichlorosilane and tetrachlorosilane obtained after distillative Cleaning separated into the pure components trichlorosilane and tetrachlorosilane can be.
Auch kann hier der HCl-Kreislauf geschlossen werden.The HCl cycle can also be closed here.
Der für die Hydrochlorierung von Silicium eingesetzte Chlorwasserstoff sollte eine möglichst hohe Reinheit besitzen, da insbesondere in Anwesenheit von organischen Verbindungen, z. B. Alkoholen, Alkylhalogeniden, Organochlorsilanen, Organosilanestern, Aminen, Olefinen sowie Wasser, im Zuge der Hydrochlorierung zur Bildung unerwünschter Nebenprodukte, wie chlorierten Aromaten, Alkylchlorsilanen, Siloxanen etc., führt, die nur mit erheblichem technischen Aufwand von den Zielprodukten abzutrennen sind.The hydrogen chloride used for the hydrochlorination of silicon should be one have the highest possible purity, especially in the presence of organic Connections, e.g. B. alcohols, alkyl halides, organochlorosilanes, Organosilane esters, amines, olefins and water in the course of the hydrochlorination to form unwanted by-products such as chlorinated aromatics, Alkylchlorosilanes, siloxanes etc., leads only with considerable technical effort must be separated from the target products.
Zur Vermeidung dieser Nachteile wurde bisher der zurückgewonnene Chlorwasserstoff entweder durch Neutralisation, Elektrolyse, Umsetzung von Chlor mit Wasserstoff oder durch Tieftemperaturkondensation und anschließende Verdampfung zwecks Reinigung bzw. Entfernung derartiger Verunreinigungen aufgearbeitet. Diese Reinigungsverfahren weisen erhebliche Nachteile auf.To avoid these disadvantages, the recovered was previously Hydrogen chloride either by neutralization, electrolysis, conversion of chlorine with hydrogen or by low-temperature condensation and subsequent Evaporation for cleaning or removing such contaminants worked up. These cleaning processes have considerable disadvantages.
Es bestand daher die Aufgabe, ein weiteres Verfahren bereitzustellen, das diese Nachteile mindert bzw. nicht aufweist.The object was therefore to provide a further method, this Reduces or does not have disadvantages.
Es wurde nun gefunden, dass man die oben genannten Nachteile im Wesentlichen
vermeidet, wenn man das Abgas aus dem Verfahren zur Herstellung eines
Organosilanesters,
wobei ein Chlorsilan der allgemeinen Formel I
It has now been found that the disadvantages mentioned above are essentially avoided if the exhaust gas from the process for producing an organosilane ester,
wherein a chlorosilane of the general formula I
RnSiCl4-n (I),
R n SiCl 4-n (I),
worin
R für Wasserstoff oder für eine 3-Chlorpropyl-, 3-Brompropyl-, 3-
Jodpropyl-, 3-Fluorpropyl-, 2-Chlorethyl-, 2-Bromethyl-, 2-Jodethyl-, 2-
Fluorethyl-, 4-Chlorbutyl-, 4-Brombutyl-, 4-Jodbutyl-, 4-Fluorbutyl-,
Chloraryl- oder Chlorbenzylgruppe oder für eine lineare, verzweigte oder
cyclische Alkylgruppe mit 1 bis 30 C-Atomen oder für eine Aralkylgruppe
mit 1 bis 30 C-Atomen steht und n gleich 1 oder 2 oder 3 ist,
mit einem Alkohol und/oder mindestens einem Glykol umgesetzt wird und dabei Chlorwasserstoff
entsteht,
bei tiefer Temperatur behandelt, d. h. ohne Chlorwasserstoff zu kondensieren,
dadurch reinen Chlorwasserstoff gewinnt und diesen ohne weitere Behandlung
wieder als Rohstoff, vorzugsweise bei der Herstellung von Chlorwasserstoff-
Folgeprodukten, insbesondere von Chlorsilanen, wie Trichlorsilan, Tetrachlorsilan,
Dichlorsilan, Monochlorsilan, um nur einige Beispiele zu nennen, einsetzt. Das so
gereinigte Chlorwasserstoff-Gas wird geeigneterweise mit Hilfe eines Verdichters,
z. B. einem Wälzkolben-Gebläse, direkt in den Prozess zur Hydrochlorierung von
elementarem Silicium eingespeist und dort zu Trichlorsilan und Tetrachlorsilan
umgesetzt. So erhaltenes Trichlorsilan kann in Organochlorsilane überführt werden.
Im weiteren Verlauf kann man so erhaltene Organochlorsilane unter Abspaltung von
HCl verestern, wodurch der HCl-Kreislauf in wirtschaftlicher und umweltverträglicher
Weise geschlossen werden kann.wherein
R represents hydrogen or a 3-chloropropyl, 3-bromopropyl, 3-iodopropyl, 3-fluoropropyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2-fluoroethyl, 4-chlorobutyl , 4-bromobutyl, 4-iodobutyl, 4-fluorobutyl, chloroaryl or chlorobenzyl group or for a linear, branched or cyclic alkyl group with 1 to 30 C atoms or for an aralkyl group with 1 to 30 C atoms and n is 1 or 2 or 3,
is reacted with an alcohol and / or at least one glycol and hydrogen chloride is formed,
treated at low temperature, i.e. without condensing hydrogen chloride, thereby recovering pure hydrogen chloride and recovering it as a raw material without further treatment, preferably in the production of hydrogen chloride secondary products, in particular chlorosilanes, such as trichlorosilane, tetrachlorosilane, dichlorosilane, monochlorosilane, to name but a few examples to name. The hydrogen chloride gas thus purified is suitably treated with the aid of a compressor, e.g. B. a Roots blower, fed directly into the process for the hydrochlorination of elemental silicon and converted there to trichlorosilane and tetrachlorosilane. The trichlorosilane obtained in this way can be converted into organochlorosilanes. In the further course, organochlorosilanes obtained in this way can be esterified with the elimination of HCl, as a result of which the HCl cycle can be closed in an economical and environmentally compatible manner.
Insbesondere für den direkten Wiedereinsatz von erfindungsgemäß bereit gestelltem Chlorwasserstoff-Gas aus der Veresterungsreaktion von Organochlorsilanen zur Hydrochlorierung von Silicium (Herstellung von Trichlorsilan) kann das erfindungsgemäße, technisch einfache, aber effektive und damit wirtschaftliche Verfahren zur Reinigung von HCl-haltigen Abgasen aus der Organosilanester- Herstellung verwendet werden.In particular for the direct reuse of what is provided according to the invention Hydrogen chloride gas from the esterification reaction of organochlorosilanes to Hydrochlorination of silicon (production of trichlorosilane) can do that inventive, technically simple, but effective and therefore economical Process for the purification of HCl-containing exhaust gases from the organosilane ester Manufacturing can be used.
Ferner weist das vorliegende Verfahren die eingangs genannten Nachteile des Standes der Technik nicht auf und macht in wirtschaftlicher Weise den direkten Wiedereinsatz des Chlorwasserstoffs möglich. Furthermore, the present method has the disadvantages of State of the art and does not make the direct in an economical manner Reuse of the hydrogen chloride possible.
Gleichzeitig kann dabei ein geschlossener HCl-Kreislauf geschaffen werden, der HCl-Verluste im Wesentlichen vermeidet und damit die Wirtschaftlichkeit von Hydrochlorierung (Trichlorsilan-Herstellung), Hydrosilylierung (Organochlorsilan- Herstellung) und Veresterungsreaktion (Synthese von Organosilanestern) steigert.At the same time, a closed HCl cycle can be created HCl losses essentially avoided and thus the economy of Hydrochlorination (trichlorosilane production), hydrosilylation (organochlorosilane Production) and esterification reaction (synthesis of organosilane esters) increases.
Darüber hinaus können durch die Vermeidung von unerwünschten Nebenprodukten bzw. Reststoffen bei der Hydrochlorierung sowie die vollständige Rückgewinnung des gebildeten Chlorwasserstoffs aus der Organosilanester-Herstellung die Herstellkosten in allen Prozessschritten reduziert und damit die Wirtschaftlichkeit der einzelnen Herstellprozesse erhöht werden. Durch die erfindungsgemäße Rückgewinnung der HCl und die Unterdrückung der Bildung schwerabbaubarer Chlorkohlenwasserstoffe wird auch ein weiterer Beitrag zum Umweltschutz geleistet.In addition, by avoiding unwanted by-products or residues in the hydrochlorination as well as the complete recovery of the hydrogen chloride formed from the organosilane ester production Manufacturing costs reduced in all process steps and thus the profitability of the individual manufacturing processes can be increased. By the invention Recovery of HCl and suppression of the formation of less degradable Chlorinated hydrocarbons also make another contribution to environmental protection.
Gegenstand der vorliegenden Erfindung ist somit ein Verfahren zur Reinigung eines
HCl-haltigen Abgases aus der Herstellung von Organosilanestern, wobei ein
Chlorsilan der allgemeinen Formel I
The present invention thus relates to a process for the purification of an HCl-containing exhaust gas from the production of organosilane esters, a chlorosilane of the general formula I
RnSiCl4-n (I),
R n SiCl 4-n (I),
worin
R für Wasserstoff oder für eine 3-Chlorpropyl-, 3-Brompropyl-, 3-
Jodpropyl-, 3-Fluorpropyl-, 2-Chlorethyl-, 2-Bromethyl-, 2-Jodethyl-, 2-
Fluorethyl-, 4-Chlorbutyl-, 4-Brombutyl-, 4-Jodbutyl-, 4-Fluorbutyl-,
Chloraryl-, Chlorbenzylgruppe oder für eine lineare, verzweigte oder
cyclische Alkylgruppe mit 1 bis 30 C-Atomen oder für eine Aralkylgruppe
mit 1 bis 30 C-Atomen steht und n gleich 1 oder 2 oder 3 ist,
mit mindestens einem Alkohol und/oder mindestens einem Glykol unter Bildung
eines Organosilanesters und Chlorwasserstoff umgesetzt wird und das
anfallende Abgas nachbehandelt wird, das dadurch gekennzeichnet ist, dass man
das bei Umsetzung anfallende chlorwasserstoffhaltige Abgas bei tiefer Temperatur
behandelt und dadurch Chlorwasserstoff-Gas gewinnt, einsetzt.
wherein
R represents hydrogen or a 3-chloropropyl, 3-bromopropyl, 3-iodopropyl, 3-fluoropropyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2-fluoroethyl, 4-chlorobutyl , 4-bromobutyl, 4-iodobutyl, 4-fluorobutyl, chloroaryl, chlorobenzyl group or for a linear, branched or cyclic alkyl group with 1 to 30 C atoms or for an aralkyl group with 1 to 30 C atoms and n is 1 or 2 or 3,
is reacted with at least one alcohol and / or at least one glycol to form an organosilane ester and hydrogen chloride and the resulting waste gas is aftertreated, which is characterized in that the waste gas containing hydrogen chloride obtained in the reaction is treated at a low temperature and thereby obtains hydrogen chloride gas ,
Geeigneterweise behandelt man das bei der Veresterung von Organochlorsilanen anfallende Chlorwasserstoff-haltige Abgas bei einer Temperatur im Bereich von -1 bis -85°C, vorzugsweise bei -10 bis -70°C, besonders bevorzugt bei -20 bis -40°C. Das HCl-haltige, mit organischen Verbindungen noch verunreinigte Abgas aus der Organosilanester-Herstellung, d. h., der dabei gebildete Chlorwasserstoff, wird vorzugsweise mehrfach über Rohrbündelwärmetauscher geführt und dabei die vorhandenen Verunreinigungen mehrfach auskondensiert, bis man am Eingang des HCl-Fördergebläses eine im Wesentlichen reine HCl (HCl-Gehalt < 99%) erhält. Diesen starken Reinigungseffekt erreicht man besonders bevorzugt dann, wenn der gebildete HCl-Gasstrom in mehreren Stufen bis -40°C abgekühlt wird, um selbst geringe Mengen an Alkohol etc. abzuscheiden. Um einen guten Wärmeübergang bei der Kondensation zu erreichen, können neben Graphitkondensatoren auch Kondensatoren aus Sonderlegierungen, z. B. Hastelloy-Apparate, eingesetzt werden. Darüber hinaus sollten die eingesetzten Apparate regelmäßig gereinigt werden.This is suitably dealt with in the esterification of organochlorosilanes resulting hydrogen chloride-containing exhaust gas at a temperature in the range of -1 to -85 ° C, preferably at -10 to -70 ° C, particularly preferably at -20 to -40 ° C. The HCl-containing exhaust gas that is still contaminated with organic compounds organosilane ester production, d. that is, the hydrogen chloride formed preferably performed several times over tube bundle heat exchangers and the existing contaminants condensed several times until one at the entrance of the HCl delivery blower receives an essentially pure HCl (HCl content <99%). This strong cleaning effect is particularly preferred when the HCl gas stream formed is cooled in several stages to -40 ° C to itself remove small amounts of alcohol etc. To ensure good heat transfer To achieve the condensation, graphite capacitors can also Special alloy capacitors, e.g. B. Hastelloy apparatus can be used. In addition, the equipment used should be cleaned regularly.
Bevorzugt wird das abgekühlte Gas mit Hilfe eines Wälzkolben-Gebläses verdichtet und gefördert.The cooled gas is preferably compressed using a Roots blower and promoted.
Geeigneterweise fördert man den Chlorwasserstoff in verdichteter Form bei einem Druck von 1,0000001 bis 4,0 bar abs., vorzugsweise bei einem Druck von 1,01 bis 3,0 bar abs., besonders bevorzugt bei 1,1 bis 2,0 bar abs.Suitably, one promotes the hydrogen chloride in a compressed form Pressure from 1.0000001 to 4.0 bar abs., Preferably at a pressure from 1.01 to 3.0 bar abs., Particularly preferably at 1.1 to 2.0 bar abs.
Im Allgemeinen führt man das erfindungsgemäße Verfahren derart aus, dass man das bei der Veresterung von Organochlorsilanen anfallende Abgas mittels einer Fördereinheit über ein geeignetes Kühlsystem leitet, wobei das Kühlsystem eine Temperatur von -1 bis -85°C aufweist.In general, the process according to the invention is carried out in such a way that the exhaust gas resulting from the esterification of organochlorosilanes by means of a Conveying unit via a suitable cooling system, the cooling system Has temperature from -1 to -85 ° C.
Das so erhaltene HCl-Gas, welches in der Regel neben Stickstoff lediglich noch Spuren von Alkohol und Alkylchloriden enthält (HCl-Gehalt < 99 Vol.-%), kann in vorteilhafter Weise, da nahezu frei von organischen Verunreinigungen, insbesondere als Einsatzstoff bei der Herstellung von Chlorsilanen, wie z. B. Tetrachlorsilan, Trichlorsilan, Dichlorsilan, erneut eingesetzt und damit praktisch vollständig recycliert werden. The HCl gas thus obtained, which is usually only in addition to nitrogen Contains traces of alcohol and alkyl chlorides (HCl content <99% by volume) advantageously, since almost free of organic contaminants, in particular as a feedstock in the production of chlorosilanes, such as. B. tetrachlorosilane, Trichlorosilane, dichlorosilane, used again and practically completely recycled become.
Somit ist auch Gegenstand der vorliegenden Erfindung die Verwendung eines bei der Veresterung von Organochlorsilanen mit einem Alkohol und/oder Glykol aus dem dabei anfallenden Abgas gewonnenen, vorzugsweise gasförmigen Chlorwasserstoffs als direkt verwertbarer Einsatzstoff für die Herstellung von Chlorsilanen.The present invention thus also relates to the use of a the esterification of organochlorosilanes with an alcohol and / or glycol the resulting exhaust gas, preferably gaseous Hydrogen chloride as a directly usable feedstock for the production of Chlorosilanes.
Claims (10)
RnSiCl4-n (I),
worin
R für Wasserstoff oder für eine 3-Chlorpropyl-, 3-Brompropyl-, 3- Jodpropyl-, 3-Fluorpropyl-, 2-Chlorethyl-, 2-Bromethyl-, 2-Jodethyl-, 2- Fluorethyl-, 4-Chlorbutyl-, 4-Brombutyl-, 4-Jodbutyl-, 4-Fluorbutyl-, Chloraryl-, Chlorbenzylgruppe oder für eine lineare, verzweigte oder cyclische Alkylgruppe mit 1 bis 30 C-Atomen oder für eine Aralkylgruppe mit 1 bis 30 C-Atomen steht und n gleich 1 oder 2 oder 3 ist,
mit mindestens einem Alkohol und/oder mindestens einem Glykol unter Bildung eines Organosilanesters und Chlorwasserstoff umgesetzt wird und das dabei anfallende Abgas nachbehandelt wird,
dadurch gekennzeichnet,
dass man das bei Umsetzung anfallende chlorwasserstoffhaltige Abgas bei einer Temperatur im Bereich von -1 bis -85°C behandelt und dabei Chlorwasserstoffgas gewinnt.1. A method for purifying a hydrogen chloride-containing exhaust gas from the production of organosilane esters, wherein a chlorosilane of the general formula I
R n SiCl 4-n (I),
wherein
R represents hydrogen or a 3-chloropropyl, 3-bromopropyl, 3-iodopropyl, 3-fluoropropyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2-fluoroethyl, 4-chlorobutyl , 4-bromobutyl, 4-iodobutyl, 4-fluorobutyl, chloroaryl, chlorobenzyl group or for a linear, branched or cyclic alkyl group with 1 to 30 C atoms or for an aralkyl group with 1 to 30 C atoms and n is 1 or 2 or 3,
is reacted with at least one alcohol and / or at least one glycol to form an organosilane ester and hydrogen chloride and the resulting exhaust gas is aftertreated,
characterized by
that the resulting hydrogen chloride-containing exhaust gas is treated at a temperature in the range from -1 to -85 ° C. and thereby hydrogen chloride gas is obtained.
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| DE2002103914 DE10203914C1 (en) | 2002-01-31 | 2002-01-31 | Recovery of hydrogen chloride, used directly as raw material e.g. in chlorosilane production, involves cooling waste gas from organosilane ester production from chlorosilane and alcohol and/or glycol without condensing hydrogen chloride |
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| DE2002103914 DE10203914C1 (en) | 2002-01-31 | 2002-01-31 | Recovery of hydrogen chloride, used directly as raw material e.g. in chlorosilane production, involves cooling waste gas from organosilane ester production from chlorosilane and alcohol and/or glycol without condensing hydrogen chloride |
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