DE19536934A1 - Process for working up acid resins - Google Patents

Process for working up acid resins

Info

Publication number
DE19536934A1
DE19536934A1 DE1995136934 DE19536934A DE19536934A1 DE 19536934 A1 DE19536934 A1 DE 19536934A1 DE 1995136934 DE1995136934 DE 1995136934 DE 19536934 A DE19536934 A DE 19536934A DE 19536934 A1 DE19536934 A1 DE 19536934A1
Authority
DE
Germany
Prior art keywords
characterized
acid
method according
separation
suspension
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.)
Withdrawn
Application number
DE1995136934
Other languages
German (de)
Inventor
Fritz Joachim Schmidt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Weiss & Co Leonhard GmbH
Original Assignee
Weiss & Co Leonhard GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Weiss & Co Leonhard GmbH filed Critical Weiss & Co Leonhard GmbH
Priority to DE1995136934 priority Critical patent/DE19536934A1/en
Publication of DE19536934A1 publication Critical patent/DE19536934A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/38Processes 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
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20Organic substances
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/40Inorganic substances
    • A62D2101/47Inorganic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen

Abstract

A process is disclosed for processing environmentally harmful stored acid sludge, in particular those produced in the distillation of waste oil and tar, the aim of the process being to satisfy both environmental and economic requirements. This is achieved with a process involving the following consecutive process steps: conversion of the acid sludge into a sulphuric suspension by the addition of dilute sulphuric acid; addition of an oxidising agent to convert any sulphide and sulphite ions to sulphate; separation of the sulphate and any solids which may be present; separation of the liquid residues into organic and inorganic fractions.

Description

The invention relates to a method for working up environmentally harmful, especially residues from a Acid resins representing waste oil or tar distillation. This Kind of acid resins are toxic, malodorous and viscous eating masses, due to the process a high proportion Have sulfuric and sulfonic acids. In addition, these acid resins each have a significant proportion of heavy weight tallen, especially lead, iron and zinc.

In the past, such acid resins have been partially un protected landfills, where these landfills to ponds due to water remaining on the acid resins have trained. These landfills are set to be eliminated of the hazard potential for humans and the ecosystem represents.

There is therefore a desire to protect the aforementioned environment harmful acid resins in an environmentally friendly Work up the form and the usable content still present recover parts.  

The ways known for this so far exist to the egg the acid resin from the previously environmentally harmful Form into a more environmentally compatible landfill-compatible form and on the other hand in converting this material as Zu to burn fuel.

Both process technologies have significant disadvantages.

The conversion of the acid resin to be converted into one world-compatible landfillable form first makes a new one Centralization required. This can preferably be done via the Zu of burnt or slaked lime. Here however, there are significant exothermic reactions where sulfur dioxide is released. Free the share sulfur dioxide within environmentally acceptable limits keeping is difficult and only with considerable equipment Effort possible. Furthermore, by adding Bin determine the elutability of those contained in the acid resins pollutants are reduced. This in turn leads to an undesirable increase in the volume of the deposit Materials. This means that the landfill is environmentally compatible acid resins mentioned in the beginning are not a practically accessible route.

Also a burn of the acid resin, because of itself whose positive caloric values are possible is not unproblematic. Because of the substantial amount of sulfur  Acid and heavy metals become welded when burned field dioxide, undecomposed sulfonic acids and heavy metal emissions released. This requires an acid-proof construction the burner and the combustion chamber. Even mature, tech nisch modern filter systems can usually do this not economically coping with harmful emissions. In practice, this does not rule out combustion pretreated acid resin from ecological considerations.

Proceeding from this, the invention shows with a preparation of the generic acid resin according to the characteristic Process steps of claim i a significantly better economically sensible solution.

The solution according to the invention is based on the following ideas.

The main components of the acid resin to be processed are aliphatic hydrocarbons with traces from C-12. The Ma The maximum range is between C-20 and C-26 up to C-40. Dane Ben are aromatic hydrocarbons in one size order from i to 2%. On inorganic compounds are sulfuric acid and sulphurous acid present which too lead to a pH between about 1 and 3. As distracting Components are heavy metals that make up a share have between 0.5 and 1.0% and mainly lead Iron, zinc and chrome exist.  

In the practical implementation of the Ver Among other things, driving must be taken into account that the open working acid resins - as far as they are in ponds - different consistencies and compositions sen. With existing pond landfills of acid resins could a breakdown of the consistency of these acid resins into at at least three different phases are identified.

  • - Very easily flowable, water-containing material on the Surface of the ponds. As a rule, these are acid resin occur through contaminated excess water in one Layer thickness from a few centimeters to about one Decimeters overlaid.
  • - viscous, highly viscous material with low water hold in the deeper layers of the ponds and
  • - almost drained, non-flowable soot-like mate rial over the bottom of the ponds.

Before or together with the first method according to the invention step in which the acid resin is passed into a suspension Addition of dilute sulfuric acid is transferred to mix the three phases mentioned above. By the addition of dilute sulfuric acid is in the mixture Adjust the pH value of approx. 2 or less. The sulfur Acid is best found in the form of a 50% sulfur  acid added. This dilute sulfuric acid is convenient It is usually only made of concentrated sulfur on site acid and water provided.

An acid resin / sulfuric acid suspension is particularly suitable at a temperature of 30-80 ° C, in particular Establish 50-70 ° C.

As an oxidizing agent, the suspension is added only as much for example perhydrol (30% hydrogen peroxide) train adds that all heavy metals that are present as sulfides the corresponding sulfates to be separated are oxidized. In particular, lead sulfate is insoluble in the suspension medium Lich and fails. The amount of perhydrol to be used is preferably about 0.5 to 1% of the total amount of suspension.

In particular what is gained from the oxidation treatment Suspen is able to separate sulfate mechanically well about the same amount of gypsum or bleaching earth as Separation aid are added to perhydrol as those previously given amount. The mechanical separation of the sulfates and any other solid present in the suspension fabrics are preferably centrifuged. The abge separated sulfates, mainly lead sulfate, can be smelted or by one described for example in EP 33 78 312 Petrification processes are solidified and deposited.  

An embodiment of the invention is based on a in the flowchart shown in the drawing.

An acid-proof stirred tank 3 is filled to 45 to 50% with acid resin S. For this purpose, from a storage container 2, in the acid from a container 1 a derived concentrated sulfuric and b from a container 1 derived water produced about 50% sulfuric acid was added. The sulfuric acid is added in an amount of approx. 50% of the amount of acid resin. The amount of sulfuric acid to be supplied is to be set so that a pH of less than 2 is established in the suspension 3 which is sensitive to the stirred tank.

The mass in the stirred vessel 3 is added with stirring by means of a heating coil or, for example, a boiling tube with steam at about 30 to 80 ° C, preferably 50 to 70 ° C, heated. At this temperature, 0.5-1% Perhydrol P, based on the amount of acid resin, is added. After about 10 minutes an iodine starch paper should still show a positive effect, otherwise further perhydrol is added in individual steps of about 0.5%.

Gypsum or bleaching earth is then added as a removal aid FH in an amount corresponding to the amount of perhydrol added. After stirring for about 1 hour, the solid / liquid phases are separated by sedimentation, filtration or centrifugation, preferably using a centrifuge 4 .

The separated solid phase F, which is all solid components from the acid resin to be worked up and the lead sulfate holds, can be smelted on lead or according to that in EP 33 78 312 described petrification process solidified and depo be kidneyed. The solids can come from Erdbe constituents that are made when digging out acid resin a landfill pond with the material to be processed one arrived.

The liquid phase emerging from the centrifuge 4 of the prepared material is alternately placed in separating pears 5 a or 5 b, in which the liquid phase separates into a sulfuric acid and an organic phase. The lower sulfuric acid phase is pumped back into the reservoir 2 after separation and strengthened there with as much concentrated sulfuric acid from the container 1 a that a 50% sulfuric acid is formed in the reservoir 2 . Small portions of the organic phase do no harm here. The organic phase separated in the separating pears 5 a and 5 b as a result of the sedimentation taking place there is drained into a settling tank 6 and fed again to a waste oil distillation system in which a usable oil fraction is still distilled off. The remaining distillation residue D can then be disposed of in an environmentally friendly manner.

Claims (8)

1. Process for working up environmentally harmful, in particular residues from a waste oil or tar distillation representing acid resins, characterized by the following treatment steps given in chronological order
  • Converting the acid resin into a sulfuric acid suspension by adding dilute sulfuric acid,
  • Adding an oxidizing agent to convert existing sulfide and sulfite ions to sulfate,
  • Separation of the sulfate and any solids present,
  • - Separation of the remaining liquid components into organic and non-organic components.
2. The method according to claim 1, characterized, that the remaining non-organic liquid sulfuric acid proportion as diluted sulfuric acid to the processing plant drive in the cycle to convert the acid resin into a Suspension is fed again.  
3. The method according to claim 1 or 2, characterized, that the organic portion remaining as residue ther is disposed of as a mixture.
4. The method according to any one of the preceding claims, characterized, that the added oxidizing agent persulfuric acid, Alka Li or alkaline earth peroxide or hydrogen peroxide (Perhy drol) is.
5. The method according to any one of the preceding claims, characterized, that the production, processing and processing of the suspension Temperatures of 30-80 ° C, preferably 50-70 ° C, he follows.
6. The method according to any one of the preceding claims, characterized, that the separation of the solids mechanically and preferably se by centrifugation.
7. The method according to any one of the preceding claims, characterized,  that to separate existing solids and sulfate a solid from the liquid constituents of the suspension Removal aid is added.
8. The method according to claim 7, characterized, that the separation aid is gypsum or bleaching earth.
DE1995136934 1995-10-04 1995-10-04 Process for working up acid resins Withdrawn DE19536934A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE1995136934 DE19536934A1 (en) 1995-10-04 1995-10-04 Process for working up acid resins

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1995136934 DE19536934A1 (en) 1995-10-04 1995-10-04 Process for working up acid resins
PCT/DE1996/001704 WO1997012647A1 (en) 1995-10-04 1996-09-07 Process for processing acid resins sludge

Publications (1)

Publication Number Publication Date
DE19536934A1 true DE19536934A1 (en) 1997-04-10

Family

ID=7773987

Family Applications (1)

Application Number Title Priority Date Filing Date
DE1995136934 Withdrawn DE19536934A1 (en) 1995-10-04 1995-10-04 Process for working up acid resins

Country Status (2)

Country Link
DE (1) DE19536934A1 (en)
WO (1) WO1997012647A1 (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD219167A1 (en) * 1983-11-25 1985-02-27 Grotewohl Boehlen Veb Process for the neutralization and destruction of organically polluted sulfuric acid

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3957676A (en) * 1972-09-22 1976-05-18 The United States Of America As Represented By The United States Energy Research And Development Administration Chemical digestion of low level nuclear solid waste material
JPS6155079B2 (en) * 1977-01-14 1986-11-26 Jgc Corp
JPS5449982A (en) * 1977-09-28 1979-04-19 Hitachi Ltd Regenerating method for ion exchange resin
JPS58161898A (en) * 1982-03-19 1983-09-26 Nippon Atomic Ind Group Co Chemical decomposition of radioactive ion exchange resin
JPH01170899A (en) * 1987-12-25 1989-07-05 Fuji Electric Co Ltd Oxidation decomposition treatment of radioactive ion exchange resin
IT1244763B (en) * 1991-03-08 1994-08-08 Enichem Sintesi Oxidative destruction process for the elimination of toxic organic substances

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD219167A1 (en) * 1983-11-25 1985-02-27 Grotewohl Boehlen Veb Process for the neutralization and destruction of organically polluted sulfuric acid

Also Published As

Publication number Publication date
WO1997012647A1 (en) 1997-04-10

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Legal Events

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OM8 Search report available as to paragraph 43 lit. 1 sentence 1 patent law
8139 Disposal/non-payment of the annual fee