EP0035198A2 - Process for the regeneration of chlorinated hydrocarbons used in dry-cleaning - Google Patents

Process for the regeneration of chlorinated hydrocarbons used in dry-cleaning Download PDF

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Publication number
EP0035198A2
EP0035198A2 EP81101259A EP81101259A EP0035198A2 EP 0035198 A2 EP0035198 A2 EP 0035198A2 EP 81101259 A EP81101259 A EP 81101259A EP 81101259 A EP81101259 A EP 81101259A EP 0035198 A2 EP0035198 A2 EP 0035198A2
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Prior art keywords
aluminum silicate
cleaning
solvent
filter
zeolite
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EP81101259A
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German (de)
French (fr)
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EP0035198B1 (en
EP0035198A3 (en
Inventor
Werner Grünewälder
Arnfried Koch
Walter Feldmann
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Chemische Fabrik Kreussler and Co GmbH
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Henkel AG and Co KGaA
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/02—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents
    • D06L1/10—Regeneration of used chemical baths

Definitions

  • the invention relates to a process for the treatment of chlorinated hydrocarbons in dry cleaning using alkali aluminum silicates, wherein the solvents are freed from pigment contamination during the usual filtration process and acid traces present in the solvent are simultaneously removed.
  • the chlorinated hydrocarbon solvents used in dry cleaning are stabilized by the manufacturer against premature decomposition by air, light, heat and moisture and are thus sold.
  • Amine compounds are preferably used as stabilizers.
  • the contaminated solvents are distilled and the condensate is separated from the distilled water using a water separator.
  • the exhaust air from the dry cleaning machine is passed through an activated carbon filter for solvent adsorption and this filter is regenerated by blowing it out with water vapor.
  • the solvent obtained in this way is also separated from the water in the water separator and then transferred to a collecting container.
  • the invention has for its object to adjust the solvents used in dry cleaning without special effort in terms of pH so that corrosion on the machine parts are avoided.
  • This object is achieved by using an aluminum silicate containing alkali ions instead of the filter powder (kieselguhr) customary in dry cleaning, or by using it in a mixture with kieselguhr.
  • the invention accordingly relates to a process for the treatment of chlorinated hydrocarbons in dry cleaning by filtration and distillation, characterized in that the filter mass is composed entirely or in part of a finely divided, water-insoluble, bound water-containing aluminum silicate of the general formula in the cat an alkali metal ion, x is a number from o, 7 to 1.5, y is a number from o, 8 to 6, preferably 1.3 to 4, with a particle size of essentially 1 to 100 ⁇ , the one X-ray amorphous or have a crystalline structure.
  • the aluminum silicates used according to the requirements are amorphous or crystalline natural or synthetic products.
  • the latter are preferred because they can be prepared in a known manner, for example by mutual precipitation of aqueous solutions of alkali aluminates with solutions of alkali silicates, the Kat 2 O: A1 2 0 3: Si0 2 ratio being controlled within the composition indicated by the general formula can.
  • Amorphous or crystalline aluminum silicates are created by suitable treatment of the precipitated products.
  • Zeolite HS hydrosodalite
  • Crystal form globular average particle diameter (for the range 0 - 30 ⁇ ) 4.2 / u.
  • Crystal structure mixture of zeolite NaA and zeolite HS in a ratio of approx. 1: 1;
  • Crystal shape rounded crystallites; average particle diameter (for the range 0 - 30 ⁇ ) 5.6 ⁇ .
  • the zolites can also be produced with other particle sizes, for example with particle sizes in the range from 20 to 50 ⁇ m. However, it has been shown that the filtration effect diminishes with increasing particle size.
  • the aluminum silicates are preferably used in a mixture with the kieselguhr commonly used for filtration purposes. Preferably 5-50% by weight of aluminum silicate, based on the total mixture, was used.
  • the filter powder mixture is added to the needle catcher of the cleaning machine to be washed and then washed as usual.
  • the textiles are cleaned in the practice of single- or multi-bath processes with the simultaneous use of a commercially available cleaning booster, whereby the first and / or the second bath is freed from dirt that is not dissolved in the solvent by filtration.
  • acidic solvent is returned to the weakly alkaline range. Monitoring of the solvent and the cumbersome preparation of the acidic solvent are thus eliminated, which considerably simplifies the work for the dry cleaner.
  • the process according to the invention is particularly suitable for the regeneration of trichlorethylene, tetrachlorethylene or 1,1,1-trichloroethane.
  • a cleaning test with tetrachlorethylene was carried out in an 18 kg chemical cleaning system, which was equipped with an activated carbon filter for solvent recovery and a multi-batch centrifugal filter.
  • the pH of the solvent in the clean tank was 5.5; after adding 3 g / 1 of a commercial cleaning booster (Lanadol multi (R) , a pH of 5.8 was measured.
  • a filter powder mixture consisting of 1500 g of diatomaceous earth and 75 g of the above-mentioned sodium aluminum silicate of the zeolite NaA type in the The filter was washed onto the needle catcher of the cleaning system and then, as usual, 18 kg of men's suits were cleaned and finished in a two-bath process with simultaneous filtration of the second bath.
  • the pH of the solvent is shifted from the acidic to the weakly alkaline range by the sodium aluminum silicate as filter aid.
  • Example 2 In the dry cleaning system described in Example 1, trichlorethylene was used as the solvent. A mixture of 1500 g of diatomaceous earth with 150 g of the above mixture of approximately equal parts of zeolite NaH and zeolite HS was used as filter powder. The other conditions corresponded to example 1. A total of 15 batches of heavily soiled textiles were cleaned. The pH and filter pressure values are listed in Table 3.
  • Example 2 In the dry cleaning system described in Example 1, tetrachlorethylene was used as the solvent. A mixture consisting of 1300 g of diatomaceous earth and 300 of the above-mentioned zeolite HS was used as filter powder. The other conditions were the same as in Example 1. However, 16 kg of poplin jackets were cleaned in the two-bath process with simultaneous filtration of the second bath. A total of 12 batches were cleaned using this procedure and a liquor sample was taken from the first, fourth, eighth and twelfth batch after the filtration process to determine the pH (see Table 4).
  • tetrachlorethylene was used as the solvent.
  • the pH of the solvent in the clean tank was 5.6 after the addition of 3 g / l of a commercial cleaning booster (Lanadol universal (R) ).
  • 1575 g of a sodium aluminum silicate (mixture of a zeolite NaA, zeolite NaX and zeolite HS) with a distribution maximum in the range 20-40 ⁇ were used as filter powder and then, as usual, 18 kg trousers were cleaned in a one-bath process with simultaneous filtration and finished as usual.
  • a sample was taken to determine the pH.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Detergent Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

1. A process for regenerating chlorinated hydrocarbons in dry-cleaning by filtration and distallation, characterized in that the filter mass consists wholly or in part of a finely particulate, water-insoluble aluminium silicate containing bound water and corresponding to the following general formula (Cat2 O)x .Al2 O3 .(SiO2 )y , in which Cat is an alkali metal ion, x is a number of from 0.7 to 1.5, y is a number of from 0.8 to 6 and preferably from 1.3 to 4, said aluminium silicate having an X-ray amorphous or crystalline structure and a particle size of subtantially 1 to 100 mu.

Description

Die Erfindung betrifft ein Verfahren zur Aufbereitung von chlorierten Kohlenwasserstoffen in der Chemischreinigung unter Verwendung von Alkalialuminiumsilikaten, wobei die Lösungsmittel während des üblichen Filtrationsvorganges von Pigmentverschmutzungen befreit und gleichzeitig im Lösungsmittel vorhandene Säurespuren beseitigt werden.The invention relates to a process for the treatment of chlorinated hydrocarbons in dry cleaning using alkali aluminum silicates, wherein the solvents are freed from pigment contamination during the usual filtration process and acid traces present in the solvent are simultaneously removed.

Die in der Chemischreinigung verwendeten Lösungsmittel vom Typ chlorierte Kohlenwässerstoffe werden vom Hersteller gegen vorzeitige Zersetzung durch Luft, Licht, Wärme und Feuchtigkeit stabilisiert und gelangen so in den Handel. Als Stabilisatoren werden vorzugsweise Aminverbindungen verwendet.The chlorinated hydrocarbon solvents used in dry cleaning are stabilized by the manufacturer against premature decomposition by air, light, heat and moisture and are thus sold. Amine compounds are preferably used as stabilizers.

In der Praxis der Chemischreinigung werden die verschmutzten Lösungsmittel destilliert und das.Kondensat über einen Wasserabscheider vom überdestillierten Wasser abgetrennt. Die Abluft der Chemischreinigungsmaschine wird zur Lösungsmitteladsorption durch ein Aktivkohlefilter geführt und dieses Filter durch Ausblasen mit Wasserdampf wieder regeneriert. Auch das hierbei gewonnene Lösungsmittel wird im Wasserabscheider vom Wasser getrennt und dann in einen Auffangbehälter übergeführt.In the chemical cleaning practice, the contaminated solvents are distilled and the condensate is separated from the distilled water using a water separator. The exhaust air from the dry cleaning machine is passed through an activated carbon filter for solvent adsorption and this filter is regenerated by blowing it out with water vapor. The solvent obtained in this way is also separated from the water in the water separator and then transferred to a collecting container.

Beide Maßnahmen führen zu einem Destillat, das mit steigender Zahl der Rückgewinnungsvorgänge zunehmend an Stabilisator verarmt und dann auf Grund von Säurebildung zu Korrosionen der Chemischreingungsmaschinen führt, wodurch kostspielige Reparaturen notwendig werden. Zur Vermeidung dieser Schwierigkeiten wird daher eine laufende Überwachung des pH-Wertes empfohlen. Fällt der pH-Wert des Lösungsmittels unter 6, so wird eine Aufarbeitung des gesamten Lösungsmittels unerläßlich. Bei Verwendung von Trichlor- oder Tetrachlorethylen muß zunächst die gesamte Reinigungsanlage mit Sodalösung durchgespült und danach das Lösungsmittel unter Zusatz von Schlämmkreide oder gelöschtem Kalk destilliert und mit Lösungsmittel vermischt werden. 1,1,1-Trichlorethan wird mit Sodalösung neutralisiert und nach Abtrennung der wäßrigen Schicht und Destillation mit frischem Lösungsmittel vermischt. Diese Arbeiten sind sehr zeitaufwendig und werden deshalb vom Chemischreiniger nur äußerst ungern vorgenommen.Both measures lead to a distillate which, with an increasing number of recovery processes, increasingly depletes the stabilizer and then, due to the formation of acid, leads to corrosion of the chemical cleaning machines, which necessitates expensive repairs. To avoid these difficulties, it is therefore recommended to monitor the pH value on an ongoing basis. If the pH of the solvent falls below 6, the entire solvent has to be worked up. When using trichlorethylene or tetrachlorethylene, the entire cleaning system must first be rinsed with soda solution and then the solvent distilled with the addition of sludge chalk or slaked lime and mixed with solvent. 1,1,1-trichloroethane is neutralized with sodium carbonate solution and, after the aqueous layer has been separated off and distilled, mixed with fresh solvent. This work is very time-consuming and is therefore extremely difficult for the chemical cleaner to undertake.

Der Erfindung liegt die Aufgabe zugrunde, die in der Chemischreinigung verwendeten Lösungsmittel ohne besonderen Arbeitsaufwand hinsichtlich des pH-Wertes so einzustellen, daß Korrosionen an den Maschinenteilen vermieden werden.The invention has for its object to adjust the solvents used in dry cleaning without special effort in terms of pH so that corrosion on the machine parts are avoided.

Diese Aufgabe wird dadurch gelöst, daß man anstelle des in der Chemischreinigung üblichen Filterpulvers (Kieselgur) ein Alkaliionen enthaltendes Aluminiumsilikat einsetzt oder dieses in Mischung mit Kieselgur verwendet.This object is achieved by using an aluminum silicate containing alkali ions instead of the filter powder (kieselguhr) customary in dry cleaning, or by using it in a mixture with kieselguhr.

Gegenstand der Erfindung ist demgemäß ein Verfahren zur Aufbereitung von chlorierten Kohlenwasserstoffen in der Chemischreinigung durch Filtration und Destillation, dadurch gekennzeichnet, daß die Filtermasse ganz oder zum Teil aus einem feinteiligen, wasserunlöslichen, gebundenes Wasser enthaltenden Aluminiumsilikat der allgemeinen Formel

Figure imgb0001
in der Kat ein Alkalimetallion, x eine Zahl von o,7 bis 1,5, y eine Zahl von o,8 bis 6, vorzugsweise 1,3 bis 4, bedeuten, mit einer Partikelgröße von im wesentlichen 1 bis 1oo µ, die eine röntgenamorphe oder eine kristalline Struktur aufweisen, besteht.The invention accordingly relates to a process for the treatment of chlorinated hydrocarbons in dry cleaning by filtration and distillation, characterized in that the filter mass is composed entirely or in part of a finely divided, water-insoluble, bound water-containing aluminum silicate of the general formula
Figure imgb0001
 in the cat an alkali metal ion, x is a number from o, 7 to 1.5, y is a number from o, 8 to 6, preferably 1.3 to 4, with a particle size of essentially 1 to 100 μ, the one X-ray amorphous or have a crystalline structure.

Die anspruchsgemäß verwendeten Aluminiumsilikate sind amorphe oder kristalline natürliche oder synthetische Produkte. Letztere sind bevorzugt, weil sie sich in bekannter Weise, z.B. durch gegenseitige Fällung wäßriger Lösungen von Alkalialuminaten mit Lösungen von Alkalisilikaten herstellen lassen, wobei das Verhältnis Kat2O : A1203 : Si02 innerhalb der durch die allgemeine Formel angegebenen Zusammensetzung gesteuert werden kann. Amorphe oder kristalline Aluminiumsilikate entstehen durch geeignete Behandlung der gefällten Produkte.The aluminum silicates used according to the requirements are amorphous or crystalline natural or synthetic products. The latter are preferred because they can be prepared in a known manner, for example by mutual precipitation of aqueous solutions of alkali aluminates with solutions of alkali silicates, the Kat 2 O: A1 2 0 3: Si0 2 ratio being controlled within the composition indicated by the general formula can. Amorphous or crystalline aluminum silicates are created by suitable treatment of the precipitated products.

Bevorzugt verwendet werden kristalline Aluminiumsilikate, bei denen Kat Natrium bedeutet. Insbesondere haben sich folgende Produkte als geeignet erwiesen:Crystalline aluminum silicates in which Kat means sodium are preferably used. The following products have proven to be particularly suitable:

Zeolith NaA:Zeolite NaA:

Ein typisches, gut geeignetes Produkt in Pulverform hat die Zusammensetzung:0,99 Na2O · 1,00 Al2O3 · 1,83 SiO2 · 4,0 H20 (= 20,9 % H20); Kristallform: kubisch mit stark abgerundeten Ecken und Kanten; mittlerer Teilchendurchmesser (für den Bereich 0 - 30/u, d.h. alle Teilchen sind kleiner als 30µ): 5,4µ.A typical, well suited product in powder form has the composition: 0.99 Na 2 O · 1.00 Al 2 O 3 · 1.83 SiO 2 · 4.0 H 2 0 (= 20.9% H 2 0); Crystal shape: cubic with very rounded corners and edges; average particle diameter (for the range 0 - 30 / u, ie all particles are smaller than 30µ): 5.4µ.

Zeolith HS (Hydrosodalith):Zeolite HS (hydrosodalite):

Ein typisches, gut geeignetes Produkt in Pulverform hat die Zusammensetzung 1,31 Na2O · 1 A1203 · 1,95 SiO2 · 2,7 H20 (= 13,9 % H20)A typical, well-suitable product in powder form has the composition 1.31 Na 2 O · 1 A1203 · 1.95 SiO 2 · 2.7 H 2 0 (= 13.9% H 2 0)

Kristallform: Kugelhaufen mittlerer Teilchendurchmesser (für den Bereich 0 - 30µ) 4,2/u.Crystal form: globular average particle diameter (for the range 0 - 30µ) 4.2 / u.

Zeolith NaA/HS-Gemisch:Zeolite NaA / HS mixture:

Ein typisches, durch direkte Synthese erhaltenes Mischprodukt hat die Zusammensetzung: 1,11 Na2O · 1 Al2O3 · 1,89 SiO2 · 3,1 H20 (= 16,4 % H2O);A typical, obtained by direct synthesis mixed product has the composition: 1.11 Na 2 O · 1 Al 2 O 3 · 1.89 SiO 2 · 3.1 H 2 0 (= 16.4% H 2 O);

Kristallstruktur: Gemisch aus Zeolith NaA und Zeolith HS im Verhältnis von ca. 1 : 1;Crystal structure: mixture of zeolite NaA and zeolite HS in a ratio of approx. 1: 1;

Kristallform: abgerundete Kristallite; mittlerer Teilchendurchmesser (für den Bereich 0 - 30µ) 5,6µ.Crystal shape: rounded crystallites; average particle diameter (for the range 0 - 30µ) 5.6µ.

Die Zolithe können auch mit anderen Teilchengrößen hergestellt werden, beispielsweise mit Teilchengrößen im Bereich von 20 - 50µ. Es hat sich jedoch gezeigt, daß die Filtrationswirkung mit zunehmender Teilchengröße nachläßt.The zolites can also be produced with other particle sizes, for example with particle sizes in the range from 20 to 50 μm. However, it has been shown that the filtration effect diminishes with increasing particle size.

Die Produkte sind auf Grund ihres Gehaltes an austauschbaren Alkaliionen imstande, die durch Zersetzung der Chlorkohlenwasserstoffe gebildeten Säuren zu neutralisieren.Due to their content of exchangeable alkali ions, the products are able to neutralize the acids formed by the decomposition of the chlorinated hydrocarbons.

Die Aluminiumsilikate werden vorzugsweise im Gemisch mit dem für Filtrationszwecke üblicherweise verwendeten Kieselgur eingesetzt. Vorzugsweise wurden 5 - 50 Gew.% an Aluminiumsilikat, bezogen auf die Gesamtmischung verwendet.The aluminum silicates are preferably used in a mixture with the kieselguhr commonly used for filtration purposes. Preferably 5-50% by weight of aluminum silicate, based on the total mixture, was used.

Das Filterpulvergemisch wird bei Ein- oder Mehrchargenfiltern zum Anschwemmen in den Nadelfänger der Reinigungsmaschine gegeben und dann wie üblich angeschwemmt. Die Reinigung der Textilien erfolgt in den in der Praxis üblichen Ein- oder Mehrbad-Verfahren bei gleichzeitiger Anwendung eines handelsüblichen Reinigungsverstärkers, wobei.das erste und/oder auch das zweite Bad durch Filtration von den nicht im Lösungsmittel gelösten Verschmutzungen befreit wird. Gleichzeitig wird sauer reagierendes Lösungsmittel wieder in den schwach alkalischen Bereich übergeführt. Eine Überwachung des Lösungsmittels und die umständliche Aufbereitung des sauren Lösungsmittels entfällt somit, wodurch die Arbeit für den Chemischreiniger erheblich erleichtert wird.In the case of single-batch or multi-batch filters, the filter powder mixture is added to the needle catcher of the cleaning machine to be washed and then washed as usual. The textiles are cleaned in the practice of single- or multi-bath processes with the simultaneous use of a commercially available cleaning booster, whereby the first and / or the second bath is freed from dirt that is not dissolved in the solvent by filtration. At the same time, acidic solvent is returned to the weakly alkaline range. Monitoring of the solvent and the cumbersome preparation of the acidic solvent are thus eliminated, which considerably simplifies the work for the dry cleaner.

Das erfindungsgemäße Verfahren eignet sich insbesondere zur Regenerierung von Trichlorethylen, Tetrachlorethylen oder 1,1,1-Trichlorethan.The process according to the invention is particularly suitable for the regeneration of trichlorethylene, tetrachlorethylene or 1,1,1-trichloroethane.

Beispiel 1example 1

In einer 18 kg-Chemischreinigungsanlage, die mit einem Aktivkohlefilter zur Lösungsmittel-Rückgewinnung und einem Mehrchargen-Schleuderfilter ausgestattet war, wurde ein Reinigungsversuch mit Tetrachlorethylen durchgeführt. Der pH-Wert des Lösungsmittels im Reintank betrug 5,5; nach Zugabe von 3 g/1 eines handelsüblichen Reinigungsverstärkers (Lanadol multi(R) wurde ein pH-Wert von 5,8 gemessen. Nach Zudosierung eines Filterpulvergemisches, bestehend aus 1500 g Kieselgur und 75 g des oben angegebenen Natriumaluminiumsilikates vom Typ Zeolith NaA in den Nadelfänger der Reinigungsanlage wurde das Filter angeschwemmt und dann wie üblich 18 kg Herrenanzüge im Zweibad-Verfahren bei gleichzeitiger Filtration des zweiten Bades gereinigt und fertiggestellt. Nach Beendigung des Filtrationsvorganges wurde der Filterdruck bestimmt und eine Probe des Lösungsmittels zur pH-Bestimmung entnommen. Die gefundenen Werte sind in Tabelle 1 enthalten. Insgesamt wurden 20 Chargen Textilien gereinigt, wobei eine Dosierung von 360 g des handelsüblichen Reinigungsverstärkers jeweils zum zweiten Bad erfolgte.A cleaning test with tetrachlorethylene was carried out in an 18 kg chemical cleaning system, which was equipped with an activated carbon filter for solvent recovery and a multi-batch centrifugal filter. The pH of the solvent in the clean tank was 5.5; after adding 3 g / 1 of a commercial cleaning booster (Lanadol multi (R) , a pH of 5.8 was measured. After metering in a filter powder mixture consisting of 1500 g of diatomaceous earth and 75 g of the above-mentioned sodium aluminum silicate of the zeolite NaA type in the The filter was washed onto the needle catcher of the cleaning system and then, as usual, 18 kg of men's suits were cleaned and finished in a two-bath process with simultaneous filtration of the second bath. After the filtration process had ended, the filter pressure was determined and a sample of the solvent was taken for pH determination. The values found are contained in Table 1. A total of 20 batches of textiles were cleaned, with a dosage of 360 g of the commercially available cleaning amplifier being carried out in each case in the second bath.

Zum Vergleich wurde in der beschriebenen Reinigungsanlage eine gleichartige Reinigung unter Zugabe von 1575 g Kieselgur, ohne Natriumaluminiumsilikat, durchgeführt. Es wurden ebenfalls 20 Chargen Textilien gereinigt. Die pH-Werte der Flotte sowie die Filterdruckwerte finden sich ebenfalls in Tabelle 1.For comparison, a similar cleaning was carried out in the cleaning system described with the addition of 1575 g of diatomaceous earth, without sodium aluminum silicate. 20 batches of textiles were also cleaned. The pH values of the liquor and the filter pressure values can also be found in Table 1.

Figure imgb0002
Aus der Tabelle ist ersichtlich, daß bei Anwendung von Natriumaluminiumsilikat als Filterpulverkomponente der pH-Wert aus dem sauren Bereich in den alkalischen Bereich übergeführt wird ohne daß sich die Filterleistung spürbar vermindert.
Figure imgb0002
 From the table it can be seen that when sodium aluminum silicate is used as the filter powder component, the pH value is converted from the acidic range to the alkaline range without the filter performance being noticeably reduced.

Beispiel 2Example 2

In einer 9 kg-Chemischreinigungsmaschine, die mit einem Mehrchargen-Kerzenfilter ausgestattet war, wurde das im Reintank befindliche 1,1,1-Trichlorethan zunächst in die Trommel und in das entleerte Filter gepumpt. Zur homogenen Vermischung zirkulierte dieses Lösungsmittel 5 Minuten. Der pH-Wert des Lösungsmittels betrug 5.2. Nach Zugabe von 3 g/1 eines handelsüblichen Reinigungsverstärkers (Lanadol plus(R))betrug der pH-Wert 5.6.In a 9 kg dry cleaning machine, which was equipped with a multi-batch candle filter, the 1,1,1-trichloroethane in the clean tank was first pumped into the drum and into the empty filter. This solvent circulated for 5 minutes for homogeneous mixing. The pH of the solvent was 5.2. After adding 3 g / 1 of a commercially available cleaning booster (Lanadol plus (R) ), the pH was 5.6.

Anschließend wurden 400 g Kieselgur mit 400 g des oben angegebenen Natriumaluminiumsilikats Zeolith HS vermischt, in den Nadelfänger der Reinigungsanlage gegeben und das Filter angeschwemmt.Then 400 g of diatomaceous earth were mixed with 400 g of the above-mentioned sodium aluminum silicate zeolite HS, placed in the needle trap of the cleaning system and the filter washes.

In der so vorbereiteten Chemischreinigungsanlage wurden 12 Chargen zu je 8 kg weiße und hellfarbige Textilien im Einbad-Verfahren bei gleichzeitiger Filtration gereinigt, wobei ca. 3o Vol.% der Reinigungsflotte jeweils ausdestilliert wurden. Der Lösungsmittelverlust wurde durch Ergänzung aus dem Destillattank (Reintank) wieder ausgeglichen. Bei der zweiten und den folgenden Chargen wurden jeweils 16o g des Reinigungsverstärkers nachgesetzt. Nach Beendigung des Reinigungsvorganges wurde der pH-Wert des Lösungsmittels und der Filterdruck ermittelt. Die Werte sind in Tabelle 2 enthalten.In the chemical cleaning system prepared in this way, 12 batches of 8 kg each of white and light-colored textiles were cleaned in a one-bath process with simultaneous filtration, with about 30% by volume of the cleaning liquor being distilled out in each case. The loss of solvent was compensated for by replenishing from the distillate tank (clean tank). In the second and subsequent batches, 16o g of the cleaning booster were added. After the cleaning process, the pH of the solvent and the filter pressure were determined. The values are shown in Table 2.

Zum Vergleich wurden in der beschriebenen Reinigungsanlage 12 Chargen zu je 8 kg weiße und hellfarbige Oberbekleidung gereinigt und fertiggestellt, wobei jedoch als Filterpulver lediglich 800 g Kieselgur eingesetzt wurden.For comparison, 12 batches of 8 kg each of white and light-colored outer clothing were cleaned and finished in the cleaning system described, but only 8 00 g of diatomaceous earth were used as filter powder.

Die ermittelten pH- und Filterdruckwerte finden sich ebenfalls in Tabelle 2.

Figure imgb0003
The determined pH and filter pressure values can also be found in Table 2.
Figure imgb0003

Wie aus Tabelle 2 ersichtlich ist, wird der pH-Wert des Lösungsmittels durch das Natriumaluminiumsilikat als Filterhilfsmittel vom sauren in den schwach alkalischen Bereich verschoben.As can be seen from Table 2, the pH of the solvent is shifted from the acidic to the weakly alkaline range by the sodium aluminum silicate as filter aid.

Beispiel 3Example 3

In der in Beispiel 1 beschriebenen Chemischreinigungsanlage wurde als Lösungsmittel Trichlorethylen eingesetzt. Als Filterpulver wurde eine Mischung aus 1500 g Kieselgur mit 150 g des oben angegebenen Gemisches aus etwa gleichen Teilen Zeolith NaH und Zeolith HS verwendet. Die anderen Bedingungen entsprachen Beispiel 1. Gereinigt wurden insgesamt 15 Chargen stark verschmutzter Textilien. Die pH- und die Filterdruckwerte sind in Tabelle 3 aufgeführt.In the dry cleaning system described in Example 1, trichlorethylene was used as the solvent. A mixture of 1500 g of diatomaceous earth with 150 g of the above mixture of approximately equal parts of zeolite NaH and zeolite HS was used as filter powder. The other conditions corresponded to example 1. A total of 15 batches of heavily soiled textiles were cleaned. The pH and filter pressure values are listed in Table 3.

Zum Vergleich wurde eine entsprechende Reinigung, jedoch lediglich auf 1650 g Kieselgur als Anschwemmfilter, durchgeführt. Die Ergebnisse der pH- und Filterdruckmessungen finden sich ebenfalls in Tabelle.3.

Figure imgb0004
For comparison, a corresponding cleaning, but only to 165 0 g of diatomaceous earth as a precoat performed. The results of the pH and filter pressure measurements can also be found in Table 3.
Figure imgb0004

Aus der vorstehenden Tabelle ist ersichtlich, daß durch die Anwendung des Natriumaluminiumsilikates als Filterhilfsmittel das Trichlorethylen aus dem sauren in den alkalischen Bereich übergeführt wird ohne Verschlechterung der Filterleistung der Reinigungsanlage.From the table above it can be seen that the use of sodium aluminum silicate as a filter aid converts the trichlorethylene from the acidic to the alkaline range without deteriorating the filter performance of the cleaning system.

Beispiel 4Example 4

In der in Beispiel 1 beschriebenen Chemischreinigungsanlage wurde als Lösungsmittel Tetrachlorethylen eingesetzt. Als Filterpulver wurde ein Gemisch, bestehend aus 1300 g Kieselgur und 300 des oben angegebenen Zeoliths HS verwendet. Die anderen Bedingungen waren die gleichen wie in Beispiel 1. Gereinigt wurden jedoch 16 kg Popelinemäntel im Zweibad-Verfahren bei gleichzeitiger Filtration des zweiten Bades. Insgesamt wurden 12 Chargen nach dieser Arbeitsweise gereinigt und bei der ersten, vierten, achten und zwölften Charge jeweils eine Flottenprobe nach Beendigung des Filtrationsvorganges zur pH-Wertbestimmung entnommen (vgl. Tabelle 4).In the dry cleaning system described in Example 1, tetrachlorethylene was used as the solvent. A mixture consisting of 1300 g of diatomaceous earth and 300 of the above-mentioned zeolite HS was used as filter powder. The other conditions were the same as in Example 1. However, 16 kg of poplin jackets were cleaned in the two-bath process with simultaneous filtration of the second bath. A total of 12 batches were cleaned using this procedure and a liquor sample was taken from the first, fourth, eighth and twelfth batch after the filtration process to determine the pH (see Table 4).

Zum Vergleich wurde ein Reinigungsversuch in gleicher Weise, jedoch mit 16oo g Kieselgur als Anschwemmfilter, durchgeführt. Die gemessenen pH-Werte sind ebenfalls in Tabelle 4 angegeben.

Figure imgb0005
For comparison, a cleaning test was carried out in the same way, but with 16oo g of diatomaceous earth as a precoat filter. The measured pH values are also shown in Table 4.
Figure imgb0005

Es ist erkennbar, daß bei Anwendung des Zeoliths HS als Filterpulverbestandteil der pH-Wert des sauren Lösungsmittels in den alkalischen.Bereich überführt wird.It can be seen that when the zeolite HS is used as a filter powder component, the pH of the acidic solvent is converted to the alkaline range.

Beispiel 5Example 5

In der in Beispiel 1 beschriebenen Chemischreinigungsanlage wurde als Lösungsmittel Tetrachlorethylen eingesetzt. Der pH-Wert des Lösungsmittels im Reintank betrug nach Zugabe von 3 g/l eines handelsüblichen Reinigungsverstärkers (Lanadol universal(R)) 5,6. Als Filterpulver wurden 1575 g eines Natriumaluminiumsilikates (Gemisch eines Zeolith NaA, Zeolith NaX und Zeolith HS) mit einem Verteilungsmaximum im Bereich 20 - 40 µ eingesetzt und dann wie üblich 18 kg Hosen im Einbad-Verfahren bei gleichzeitiger Filtration gereinigt und wie üblich fertiggestellt. Beim Abpumpen der Flotte in die Destillierblase wurde eine Probe zur Bestimmung des pH-Wertes entnommen.In the dry cleaning system described in Example 1, tetrachlorethylene was used as the solvent. The pH of the solvent in the clean tank was 5.6 after the addition of 3 g / l of a commercial cleaning booster (Lanadol universal (R) ). 1575 g of a sodium aluminum silicate (mixture of a zeolite NaA, zeolite NaX and zeolite HS) with a distribution maximum in the range 20-40 μ were used as filter powder and then, as usual, 18 kg trousers were cleaned in a one-bath process with simultaneous filtration and finished as usual. When the liquor was pumped out into the still, a sample was taken to determine the pH.

Zum Vergleich wurde in der gleichen Reinigungsanlage nach Ausdestillation der Gesamtflotte und erneuter Zugabe von 3 g/l des gleichen Reinigungsverstärkers ein Anfangs-pH-Wert von 5,8 ermittelt. Danach wurde eine gleichartige Reinigung unter Zugabe von 1575 g Kieselgur durchgeführt. Auch hier wurde nach Ablauf der Reinigung eine Flottenprobe zur pH-Wertbestimmung entnommen. Die Werte sind in Tabelle 5 enthalten.

Figure imgb0006
For comparison, an initial pH of 5.8 was determined in the same cleaning system after distilling out the entire liquor and adding 3 g / l of the same cleaning booster again. A similar cleaning was then carried out with the addition of 1575 g of diatomaceous earth. Here, too, a liquor sample was taken to determine the pH after cleaning. The values are shown in Table 5.
Figure imgb0006

Es ist erkennbar, daß bei Verwendung des Natriumaluminiumsilikats als Filterpulver das Lösungsmittel in den alkalischen Bereich überführt wird.It can be seen that when the sodium aluminum silicate is used as the filter powder, the solvent is converted into the alkaline range.

Claims (7)

1. Verfahren zur Aufbereitung von chlorierten Kohlenwasserstoffen in der Chemischreinigung durch Filtration und Destillation, dadurch gekennzeichnet, daß die Filtermasse ganz oder zum Teil aus einem feinteiligen, wasserunlöslichen, gebundenes Wasser enthaltenden Aluminiumsilikat der allgemeinen Formel
Figure imgb0007
in der Kat ein Alkalimetallion, x eine Zahl von o,7 bis 1,5, y eine Zahl von o,8 bis 6, vorzugsweise 1,3 bis 4, bedeuten, mit einer Partikelgröße von im wesentlichen 1 bis 1oo p, die eine röntgenamorphe oder eine kristalline Struktur aufweisen, besteht.1. A process for the treatment of chlorinated hydrocarbons in dry cleaning by filtration and distillation, characterized in that the filter mass is wholly or partly made of a finely divided, water-insoluble, bound water-containing aluminum silicate of the general formula
Figure imgb0007
 in the cat an alkali metal ion, x is a number from o, 7 to 1.5, y is a number from o, 8 to 6, preferably 1.3 to 4, with a particle size of essentially 1 to 100 p, which is a X-ray amorphous or have a crystalline structure. 2. Verfahren nach Anspruch 1 unter Verwendung eines Aluminiumsilikats der angegebenen allgemeinen Formel, worin Kat Natrium ist.2. The method of claim 1 using an aluminum silicate of the general formula given, wherein Kat is sodium. 3. Verfahren nach Anspruch 1 und 2 unter Verwendung eines synthetischen Aluminiumsilikats.3. The method according to claim 1 and 2 using a synthetic aluminum silicate. 4. Verfahren nach Anspruch 1 bis 3 unter Verwendung eines kristallinen Aluminiumsilikats.4. The method according to claim 1 to 3 using a crystalline aluminum silicate. 5. Verfahren nach Anspruch 1 bis 4 unter Verwendung von Zeolith NaA oder Zeolith HS oder deren Mischungen.5. The method according to claim 1 to 4 using zeolite NaA or zeolite HS or mixtures thereof. 6. Verfahren nach Anspruch 1 bis 5 unter Verwendung einer Mischung aus einem Aluminiumsilikat der angegebenen allgemeinen Formel und Kieselgur, wobei der Anteil des Aluminiumsilikates an der Gesamtmischung 5 - 50 Gew.% beträgt.6. The method according to claim 1 to 5 using a mixture of an aluminum silicate of the specified general formula and diatomaceous earth, wherein the proportion of aluminum silicate in the total mixture is 5-50 wt.%. 7. Verfahren nach Anspruch 1 bis 6 zur Regenerierung von Trichlorethylen, Tetrachlorethylen oder 1,1,1-Trichlorethan.7. The method according to claim 1 to 6 for the regeneration of trichlorethylene, tetrachlorethylene or 1,1,1-trichloroethane.
EP81101259A 1980-02-29 1981-02-21 Process for the regeneration of chlorinated hydrocarbons used in dry-cleaning Expired EP0035198B1 (en)

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AT81101259T ATE4060T1 (en) 1980-02-29 1981-02-21 PROCESSES FOR TREATMENT OF CHLORATED HYDROCARBONS IN DRY CLEANING.

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DE19803007633 DE3007633A1 (en) 1980-02-29 1980-02-29 METHOD FOR TREATING CHLORINE CARBONATES IN CHEMICAL CLEANING
DE3007633 1980-02-29

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EP0035198A3 EP0035198A3 (en) 1981-12-23
EP0035198B1 EP0035198B1 (en) 1983-07-06

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0207366A2 (en) * 1985-06-27 1987-01-07 Henkel Kommanditgesellschaft auf Aktien Process for the filtration of dry-cleaning baths and filtration aids in the form of prepared layered silicates used thereby

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3230048A1 (en) * 1982-08-12 1984-02-16 Wacker-Chemie GmbH, 8000 München METHOD FOR STABILIZING CHLORINE HYDROCARBONS, METHOD STABILIZED CHLORINE HYDROCARBONS AND THEIR USE

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1942324A1 (en) * 1969-05-21 1970-11-26 F W Means & Company Method of treating articles of clothing
US3658459A (en) * 1968-03-06 1972-04-25 Pursol Chemical Corp Absorbent for purifying dry-cleaning solvents

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3658459A (en) * 1968-03-06 1972-04-25 Pursol Chemical Corp Absorbent for purifying dry-cleaning solvents
DE1942324A1 (en) * 1969-05-21 1970-11-26 F W Means & Company Method of treating articles of clothing

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0207366A2 (en) * 1985-06-27 1987-01-07 Henkel Kommanditgesellschaft auf Aktien Process for the filtration of dry-cleaning baths and filtration aids in the form of prepared layered silicates used thereby
EP0207366A3 (en) * 1985-06-27 1987-05-06 Henkel Kommanditgesellschaft Auf Aktien Process for the filtration of dry-cleaning baths and filtration aids in the form of prepared layered silicates used thereby
US4774004A (en) * 1985-06-27 1988-09-27 Henkel Kommanditgesellschaft Auf Aktien Process for filtering liquors used in dry cleaning

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EP0035198B1 (en) 1983-07-06
EP0035198A3 (en) 1981-12-23
ATE4060T1 (en) 1983-07-15
DE3160548D1 (en) 1983-08-11
DE3007633A1 (en) 1981-09-10

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