WO1997004899A1 - Agent de production de charbon luisant pour sables de fonderie - Google Patents

Agent de production de charbon luisant pour sables de fonderie Download PDF

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Publication number
WO1997004899A1
WO1997004899A1 PCT/DE1996/001328 DE9601328W WO9704899A1 WO 1997004899 A1 WO1997004899 A1 WO 1997004899A1 DE 9601328 W DE9601328 W DE 9601328W WO 9704899 A1 WO9704899 A1 WO 9704899A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon
residue
softening temperature
aftertreatment
reactive
Prior art date
Application number
PCT/DE1996/001328
Other languages
German (de)
English (en)
Inventor
Franz Baumgartner
Eckhard Mekus
Siegfried Steinke
Original Assignee
Hüttenes-Albertus Chemische Werke GmbH
Hüttenes-Albertus France S.A.R.L.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hüttenes-Albertus Chemische Werke GmbH, Hüttenes-Albertus France S.A.R.L. filed Critical Hüttenes-Albertus Chemische Werke GmbH
Priority to DE19680623T priority Critical patent/DE19680623D2/de
Priority to AU66105/96A priority patent/AU6610596A/en
Priority to EP96925639A priority patent/EP0783387A1/fr
Publication of WO1997004899A1 publication Critical patent/WO1997004899A1/fr

Links

Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/38—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by oxidation; by combustion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/40—Inorganic substances
    • A62D2101/47—Inorganic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
    • A62D2203/02—Combined processes involving two or more distinct steps covered by groups A62D3/10 - A62D3/40

Definitions

  • Glossy carbon formers are carbonaceous substances that are added to the foundry molding mixture in order to develop hydrocarbonaceous gases in the casting heat, which create a reducing atmosphere and create a glossy carbon film on the molding material particles, which has a favorable effect on the casting surface.
  • a typical carbon luster is hard coal dust, which, however, only forms about 10% by weight of carbon luster and, because of its risk of explosion, also gives rise to storage problems.
  • Other substances such as coal tar pitch, bitumen or synthetic resins have a higher ability to form lustrous carbon, but are difficult to grind and / or are too expensive. Mixtures of various glossy carbon formers are therefore often used as a compromise in practice.
  • DE-A 3830463 describes a step in the direction of an inexpensive carbon luster.
  • This carbon luster is based on a processed residue of phenol synthesis, has a softening temperature of 80-110 ° C. and forms 30-40% by weight carbon luster.
  • working up the residue of the phenol synthesis is quite complex and, after distillation to remove low-boiling components, requires an aftertreatment to increase the yield of glossy carbon.
  • This aftertreatment consists in mixing the destination residue with a high-boiling aromatic oil and a reflux distillation at temperatures between 320 and 360 ° C under a pressure of at least 300 mbar for 5 to 24 hours.
  • the aim of the invention is to provide the foundry technology with a particularly inexpensive bright carbon former which has a high ability to form bright carbon without the need for post-treatment to increase the yield of bright carbon.
  • This object is er ⁇ sufficient that the lustrous carbon consists essentially of a residue of the bisphenol production, low-boiling by separation Komponen ⁇ th to a softening temperature of at least 70 * C is set.
  • a softening temperature of at least 70 * C is preferably done by AbdestiHation of low-boiling components, that is in the first place of phenol.
  • the softening temperature has practically no effect on the yield of glossy carbon, but primarily affects the physical manageability of the product. Softening temperatures below 70 ° C are not excluded in principle, but are unsuitable because then the product can hardly be milled and no longer remains free-flowing during storage.
  • auxiliaries such as bentonite and / or hard coal dust can be added to the residue in order to improve the grindability and storage stability.
  • these auxiliaries have to be used in increasing quantities as the reaching temperature drops and can possibly make up up to 90% by weight of the product, as a result of which the yield of bright coal formed is correspondingly reduced. It is therefore much more advantageous to set the softening temperature of the residues to values of at least 90 ° C., as a result of which the grindability and storability is ensured even without the addition of auxiliaries.
  • a softening temperature of 90 ° C and higher can be achieved in different ways.
  • the possibility of subjecting the residues to vacuum distillation, by means of which the softening temperature can be increased to up to 130 ° C., depending on the procedure, is particularly simple and inexpensive. It is also very effective to treat the residues oxidatively or to implement them with an epoxy. This generally leads to an increase in the softening temperature of up to 30 ° compared to an initial value of around 70 ° C.
  • non-oxidative salts such as sodium carbonate or basic substances W yy Ov j 9 y 7 / / / 0u4 * 8 »9 y 9 y PCT / DE96 / 01328
  • the preferred way to set an elevated softening temperature is vacuum distillation, which can be carried out at temperatures between 150 and 300 * C and pressures in the range of 15 mbar and normally requires distillation times of only 1-2 hours. If a further improvement in odor (in combination with a further increase in the softening temperature) is then desired, oxidation, reaction with an epoxy and / or addition of salts / bases can take place in a second stage.
  • All customary oxidizing agents are suitable as oxidizing agents, air oxidations and oxidations using metal ions capable of changing valence have in many cases led to particularly good results, ecologically harmless, particularly easy to carry out and highly effective, the oxidation with a peroxo or peroxy compound, preferably a percarbonate.
  • Peroxo and peroxy compounds are generally excellent oxidizing agents, percarbonate acts simultaneously as an oxidizing agent and as a basic substance and is therefore probably particularly well suited.
  • the bright carbon former according to the invention can be used on its own as the only bright carbon former or in a mixture with other shiny carbon former.
  • An addition of polystyrene has proven to be particularly advantageous, since it also has an increasing effect on the softening temperature and the yield of bright coal.
  • a residue of bisphenol A production is adjusted to a softening temperature of 77 ° C. by the processes described at the beginning for removing low-boiling components.
  • This product also referred to below as the "base material”
  • This product has a phenol content of 11% by weight and a strong odor. It pyrolyzes very uniformly over a wide temperature range and forms 43% by weight of glossy carbon, and in this respect represents an inexpensive and highly effective glossy carbon former.
  • the softening temperature of 77 ° C requires careful avoidance of heat during the grinding and can also result in problems with the storage of the ground product, because in practice temperatures in the range of up to 50 ° C can occur in the storage silos can lead to clumping.
  • Bentonite is a suitable additive in this sense.
  • a mixture of 30% by weight of the product according to Example 1A and 70% by weight of bentonite is easy to grind and also easy to ensilage.
  • the base material according to Example 1A was refluxed at a temperature of 165 ° C. for 15 minutes and then subjected to vacuum distillation at this temperature (for 1 to 2 hours at 14 mbar).
  • the residue treated in this way had a reduced but still clearly perceptible odor.
  • His Phenol ⁇ salary had dropped from 11 wt.% To 0.34 wt.% And increased its softening vonn 77 ° C to 104 * C. He was easy to grind, the ground Zu ⁇ was readily at temperatures in the range of 50 * C stock and formed still 43 wt.% Gloss coal.
  • the residue also contained bisphenol, which can cleave back to phenol.
  • bisphenol which can cleave back to phenol.
  • a little sulfuric acid was added to the residue after the vacuum distillation and the mixture was heat-treated in a closed vessel at 170 ° C. for 24 hours. After the tempering, the softening temperature and the yield of bright coal had practically not changed, but the phenol content had risen from 0.94% by weight to just over 2% by weight as a result of bisphenol cleavage.
  • a low (residual) phenol content of the residue does not hinder the use as a glossy carbon former, especially when the molding sands are regenerated. When dumping old sands, however, higher phenol contents must be observed because phenol is a water poison.
  • the base material according to Example 1A was again subjected to vacuum distillation under the conditions described in Example 2A, but at a temperature of 230 ° C. instead of 165 ° C.
  • the residue treated in this way had a softening temperature of 128 ° C., formed (unchanged) 43% by weight of glossy carbon and no longer contained any free phenol, and no further cleavage of bisphenol (heating for 24 hours, 170 ° C.) took place, and the phenol content remained at 0.0% by weight after the heating
  • the smell of the residue was greatly reduced and barely perceptible, and grindability and shelf life (silage capacity) were very good.
  • the oxidation product was then at 180 * C for the purpose of epoxidation zusharm ⁇ Lich converted to glycidyl ether of bisphenol A with three parts by weight. After about half an hour, the softening point was determined for a sample of the epoxidation product formed, a value of 95 ° C. being obtained. A smell of the epoxidation product was no longer detectable at 180 ° C. The yield of glossy carbon was 43% by weight. This also applies to the following examples 3B and 3C, 4A and 4B and 5A, 5B, 5C and 5D. B.
  • Example 2A The procedure is as in Example 2A, but with the addition of 1.75 parts by weight of sodium percarbonate to 100 parts by weight of the liquefied base material.
  • the softening temperature of the oxidized product was 91 * C and the product epoxi ⁇ -founded at 92 * C.
  • the pH was 8.9 after the oxidation.
  • the smell of the oxidized product was low and could no longer be detected in the epoxidized product.
  • Example 3A The procedure is also as in Example 3A, but with the addition of 2.5 parts by weight of sodium percarbonate to 100 parts by weight of the liquefied base material.
  • the softening temperature of the oxidized product was 86 * C and the epoxi ⁇ -founded product at 88 ° C.
  • the pH was 9.0 after the oxidation.
  • the smell of the oxidized product was low and could no longer be detected in the epoxidized product.
  • Example 3A Carried out as in Example 3A, but instead of adding sodium percarbonate, adding a mass part of sodium carbonate (soda) to 100 ml mass parts of the liquefied base material.
  • the base material was not oxidized by the addition of soda, but only converted into a basic material. This corresponds to an increase in pH from 5.9 (base material slurry) to 10.4. Foaming of the reaction mixture of base material and soda was not observed when heating to 180 ° C. The smell of the reaction product was almost unchanged compared to the base material, ie still very strong, the softening temperature was 91 * C.
  • Example 4A Carried out as in Example 4A, but with the addition of 1.5 parts by mass of soda to 100 parts by mass of base material.
  • the smell of the reaction product with soda was still strong.
  • the pH was 10.7, and the softening temperature was 97 * C.
  • the Er ⁇ softening temperature slightly dropped to 96 * C.
  • Example 5A Carried out as in Example 5A, but with the direct addition of 5 parts by mass of bisphenol A bis-glycidyl ether to 100 parts by mass of the base material. This addition led to a particularly strong reduction in the smell, but had no effect on the softening temperature. As in Example 5A, this was 93 ° C.
  • Example 5B Carried out as in Examples 5A and 5B, but with the direct addition of 11 parts by mass of bisphenol-A-bis-glycidyl ether. Similar to Example 5B, a particularly strong reduction in odor was found. The softening temperature was again 93 ° C.
  • Example 6 Combination with polystyrene
  • the bright carbon former according to the invention according to one of the preceding examples can be easily combined with other bright carbon former, for example hard coal dust and in particular polystyrene.
  • the substances can be milled and mixed together.
  • polystyrene it is more advantageous to fuse the product according to the invention with polystyrene analogously to the process described in DE-C 33 05 745 at temperatures above 150 ° C. and to grind it after cooling.
  • a mixture of 30 parts by mass of regenerated polystyrene and 70 parts by mass of the product according to the invention was prepared by stirring the polystyrene into the still warm residue after the vacuum distillation according to Example 2A. After cooling, a product was obtained which was very easy to grind and ensilage. As a result of the high ability of polystyrene to form glossy carbon, the product gave a glossy carbon yield of 48% by weight. The softening temperature had risen to 126 ° C.
  • Example 6A Analogously to Example 6A, the product distilled at higher temperatures was fused with polystyrene according to Example 2B and ground after cooling.
  • the yield of glossy carbon increased in accordance with the contributions made by the individual components (polystyrene alone provides 60-80% by weight of polystyrene), and the softening temperature increased as follows:

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cet agent de production de charbon luisant est sensiblement constitué d'un résidu de la production de bisphénol dont la température de ramollissement est réglée sur au moins 70 °C par séparation des éléments constitutifs à bas point d'ébullition. De préférence, la température de ramollissement est réglée sur au moins 90 °C par un traitement ultérieur de distillation et/ou de réaction. Cet agent de production de charbon luisant donne plus de 40 % en poids de charbon luisant et se laisse aisément broyer et ensiler. Il peut être utilisé seul ou mélangé à d'autres agents de production de charbon luisant. De manière particulièrement appropriée, on fait fondre cet agent de production de charbon luisant avec du polystyrène et on le broie après son refroidissement.
PCT/DE1996/001328 1995-07-28 1996-07-19 Agent de production de charbon luisant pour sables de fonderie WO1997004899A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE19680623T DE19680623D2 (de) 1995-07-28 1996-07-19 Glanzkohlenstoffbildner für Giessereisande
AU66105/96A AU6610596A (en) 1995-07-28 1996-07-19 Glance coal producing agent for foundry sand
EP96925639A EP0783387A1 (fr) 1995-07-28 1996-07-19 Agent de production de charbon luisant pour sables de fonderie

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1995129030 DE19529030A1 (de) 1995-07-28 1995-07-28 Aufarbeitungsverfahren für einen Destillations-Rückstand der Bisphenol-Herstellung; aufgearbeiteter Destillations-Rückstand und Glanzkohlenstoffbildner für Gießereisande
DE19529030.5 1995-07-28

Publications (1)

Publication Number Publication Date
WO1997004899A1 true WO1997004899A1 (fr) 1997-02-13

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ID=7768916

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE1996/001328 WO1997004899A1 (fr) 1995-07-28 1996-07-19 Agent de production de charbon luisant pour sables de fonderie

Country Status (4)

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EP (1) EP0783387A1 (fr)
AU (1) AU6610596A (fr)
DE (2) DE19529030A1 (fr)
WO (1) WO1997004899A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7169941B2 (en) 2002-05-22 2007-01-30 Tokuyama Corporation Photochromic composition

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015118428A1 (de) 2015-10-28 2017-05-04 Purinvent System Gmbh Phenol-Formaldehydharz-freie Bindemittel für Gießerei-Formsande
CN109796625B (zh) * 2018-12-28 2021-11-16 南京绿金人橡塑高科有限公司 一种用于橡胶再生的环保再生剂及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5744649A (en) * 1980-09-01 1982-03-13 Mitsui Toatsu Chem Inc Resin composition suitable for shell molding
DE3830463A1 (de) * 1988-09-08 1990-03-15 Ruetgerswerke Ag Glanzkohlenstoffbildner
SU1565567A1 (ru) * 1988-08-16 1990-05-23 Государственный Проектный И Технологический Институт Кузнечно-Прессового Машиностроения Противопригарное покрытие дл литейных форм и стержней
GB2271357A (en) * 1992-09-04 1994-04-13 Mitsui Toatsu Chemicals Phenolic resin composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5744649A (en) * 1980-09-01 1982-03-13 Mitsui Toatsu Chem Inc Resin composition suitable for shell molding
SU1565567A1 (ru) * 1988-08-16 1990-05-23 Государственный Проектный И Технологический Институт Кузнечно-Прессового Машиностроения Противопригарное покрытие дл литейных форм и стержней
DE3830463A1 (de) * 1988-09-08 1990-03-15 Ruetgerswerke Ag Glanzkohlenstoffbildner
GB2271357A (en) * 1992-09-04 1994-04-13 Mitsui Toatsu Chemicals Phenolic resin composition

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8216, Derwent World Patents Index; Class A81, AN 82-32097E, XP002018226 *
DATABASE WPI Section Ch Week 9103, Derwent World Patents Index; Class A82, AN 91-020609, XP002018225 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7169941B2 (en) 2002-05-22 2007-01-30 Tokuyama Corporation Photochromic composition

Also Published As

Publication number Publication date
DE19529030A1 (de) 1997-01-30
DE19680623D2 (de) 1998-01-22
EP0783387A1 (fr) 1997-07-16
AU6610596A (en) 1997-02-26

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