FI60573B - FOERFARANDE OCH ANORDNING FOER BEHANDLING AV SUR TJAERA - Google Patents

Description

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JgflÄ lBJ (11> UTLÄGGNINGSSKRIFT 6Ui) C / 4 «Patent layännetljf iO 02 1/02 'Patent meddelat v (51) Kv.lk?/lnt.CI.3 c 10 C 1/20 SUOMI-FINLAND (21) P * t «nttih» k * mu «- PK« ntans6knlng 76l78l (22) HakemlipUvl - An * ekningtdag 18.06.7 ^ * * (23) Alkupftlvi — Glltlghtttdag l8.O6.76 (41) Tullut JulklMktl - Bllvlt offentllg 2k. 12. 76

Patent and Registration Board .... ΜΜ. . ,. ,,. „. . . . _. , (44) Date of Nihttvikilpenon * | - 0_,

Patents and registration certificates issued by the Antichrist and the Court of Appeal 30.10.8l (32) (33) (31) Pyy4 «« y «uoIImus —Begird prlorltet 2 3.06.75 21.08.75 Austria-Österrike (AT) A 1 * 786/75 A 61 * 80/75 (71) Karl Potuzak, Robert Hohenvartergasse 9, A-3002 Purkersdorf,

Karl Diehl, Märzstrasse 15, A-1150 Vienna, Austria-Austria (AT) (72) Karl Potuzak, Purkersdorf, Karl Diehl, Vienna, Karl Toth, Vienna, Austria-Austria (AT) (7l *) Leitzinger Oy, (51) This invention relates to a method and apparatus for treating acid tar obtained by refining mineral oil with acids.

The object of the present invention is to provide a method of said quality as well as an apparatus for carrying out the method, which allow the removal of said acid tar to be carried out in a manner which is economical, technically simple and not harmful to the environment.

It should be emphasized that the present invention, with respect to both the method and the apparatus for carrying it out, is a combination of the prescribed method steps and structural details which, by the cooperation described below, ensures that the desired effect is achieved.

In the past, the removal of acid tar was so difficult that cleaning with sulfuric acid and oleum often had to be stopped for this reason, even if this type of cleaning of various products was more technically expedient and economical than other cleaning methods.

Acid tar obtained from various cleanings is deposited, contrary to the efforts of 2,605,773 environmental protection, still in nature and on site coated with lime. In this case, there is a risk that the oil parts in the acid tar will seep into the groundwater and contaminate it. Gradually, these methods will no longer be allowed.

With lime neutralization and gypsum-tar-oil sludge deposit, the same drawbacks occur and it is possible at all only as an expensive special deposit.

Simply burning acid tar only creates a new problem. Instead of endangering groundwater, the process releases large amounts of SC> 2 and SO 2 into the atmosphere, which pose a danger as finely divided sulfuric acid or sulfuric acid to humans and animals and to the surrounding vegetation. Although such installations are allowed in special cases to keep immissions lower, the high chimneys required entail considerable costs. In addition, such consents are being issued in ever-decreasing numbers. Environmental protection requirements therefore make it necessary for flue gases to be cleaned of Sea and SO 4. In this case, the acids washed from the flue gases must later be neutralized and the gypsum sludge must be stored either in clay soils or loaded with suitable soluble mineral salts in the resulting highly water-conducting basins. The advantage of incineration is that the remaining residues now freed water from hazardous oil sources, and the disadvantage is that the transport of sludge is costly and the acquisition of a flue gas cleaning plant involves very large investments that increase the production cost.

The method according to the invention avoids the disadvantages presented. It is characterized in that tar is mixed with alkaline earth oxides, hydroxides or carbonates, for example lime, in the form of dry or possibly concentrated aqueous slurries, after which the semi-solid solid reaction product, preferably comminuted, is subjected to a multi-stage, preferably two-stage At a temperature of 500 ° C, while the gaseous semi-coke products formed in the second stage, possibly after mixing the initial (start-up) fuel, are burned and finally the solid semi-coke residue is removed from the semi-coker.

3,60573

The device according to the invention is characterized in that it has a storage tank for neutralizing acid tar, a neutralizing agent and possibly fillers or additives to be added to the neutralizing agent, for example used bleaching clay, a mixing device for mixing said ingredients by neutralizing the tar, a semi-coking chamber with an air supply device and a gaseous semi-coke product discharge device and a solid semi-coke residue discharge device, a combustion chamber or a condensing device connected after the half-coke device, said outlet gas being ignited and

The method according to the invention and the device for carrying it out will now be described in more detail with reference to the accompanying drawings, in which Figure 1 shows a technological diagram and Figures 2-6 show details of a mixing device according to the invention, Figure 2 shows a section of a coil-operated device; with partially removed, Fig. 4 shows the device driven by the sprockets in the same way as Fig. 2, Fig. 5 shows a section taken along the line IV-IV in Fig. 4, Fig. 6 shows a section of the device driven by the conveyor belt.

In Figure 1, reference numeral 21 denotes a silo neutralizing agent, i.e. possibly lime, for acid tar. Reference numeral 22 denotes a container for the acid tar to be separated and reference numeral 4 60573 denotes a container 31 possibly arranged for the bleaching residue used, which can be added to the neutralizing agent.

The mixing and neutralization of the acid tar with the neutralizing agent and possibly other ingredients is carried out according to the invention in a mixing device 23, the structure of which is also part of the present invention and will be explained in detail below. The gaseous products formed in this neutralization process are, as shown, introduced into and neutralized in the aqueous collection solution 30, after which the neutralized gases are discharged along line 33. As mentioned, the solid and semi-solid neutralization products, if necessary, are then passed to a milling machine marked with the reference number 24 and go from there to the first stage of heat treatment, which according to the above is a semi-coking process. A semi-coke oven or similar device in which this is carried out is indicated in Figure 1 by reference numeral 25. A semi-coking process carried out at a low temperature of 330 ° to less than 50 ° C produces gaseous products and a solid residue which is free under the stated conditions. Gaseous products. is led to the combustion chamber 26, where, as mentioned above, the auxiliary fuel passed along the line 29 and possibly the "starting fuel" at start-up can also be burned. Energy can potentially be put to good use. The flue gases go to the fireplace marked with reference number 27. The solid semi-coke residue is passed through a discharge device to the tank marked 28 and, as mentioned, for the production of fertilizer and the possible addition of other substances (in the case of burnt lime or limestone as a neutralizing agent) consisting mainly of semi-coke and gypsum to form a semi-coke residue can be carried out here. in the tank. Air can be led through line 32.

It has been mentioned above that the construction of the mixing device generally indicated by reference numeral 23 in Fig. 1 is also part of the invention. This mixing device, shown in Figures 2-6 of the drawings, essentially comprises a collection vessel with a dosing device on the inlet side for importing acid tar and a neutralizing agent such as lime and the like and a mixer on the outlet side for conveying the mixing material from the collection vessel to the outlet. Suitably, the mixing device further comprises a device for forcibly directing a small amount of vaporized sulfuric acid with the reaction water vapor through or over the mixing agent, wherein the dosing device delivers an excess of previously mixed neutralizing agent so as to achieve extensive further neutralization.

Further, a water bath 30 may optionally be connected to the mixing device 23, as shown, via a suction fan, in which the entrained acid vapors are diluted and subsequently neutralized.

All embodiments of the device have a common collecting vessel 1, a conveying and mixing device 2 (neutralizing device) and a dosing device 3. In the present case, the collecting vessel 1 is made as a funnel. Instead of a funnel, a hopper or the like can also be provided. The dosing device 3 is located on the inlet side of the collecting vessel 1 and its function is to feed acidic tar and alkaline earth products in the planned small quantities. The conveying device 2 joins the hopper 1 at the bottom and has a conveying channel 4 running horizontally and having at one end an orifice 5 in the collecting container 1 and an outlet opening 6 at the other end. In the embodiment of the device according to Figs. 8, the threads of which intersect with each other, so that in addition to the transport effect, they also complement the mutual cleaning. Both turns 7, 8 mix and grind the material they carry without the adhesion of the threads. The shafts 9, 10 are mounted on the end walls 11, 12 of the conveying channel 4 and connected to a set of gears 13 outside the funnel-side end, which is connected to a drive source, for example a motor.

the embodiment of the device of Figures 4 and 5. Instead of kierien 7, 8 are arranged grooved rollers 14 15 which are adapted to the longitudinal täisvälein and the vertical direction as seen in relation to one another MOVE-retysti and used in opposite directions, so that in addition to the handling of goods also takes place in the transport direction of arrow A .

The device according to Fig. 6 for conveying goods has an endless conveyor belt 16 extending over the entire length of the conveying channel 4, above which a mixing device 17 is arranged in connection with the above-mentioned mouth opening 5 of the conveying channel 4.

Instead of two turns, another suitable device is arranged, for example a gear chain, which interlocks with the rise of the first turn.

The advantage of the device according to the invention is the low power consumption for the mixing step. However, this auxiliary device can be constructed in such a way that the acid which evaporates with the water vapor generated in the pin in amounts is passed through or over the mixing medium. If the additions of alkaline substances (for example lime) take place stoichiometrically above the required amount, these gases are also completely or largely passed to neutralization.

It has been mentioned at the outset that the advancement and technical efficiency of the present invention are in the technically simple and economically low cost implementation of the method according to the invention, but above all in that it is not harmful to the environment. This is illustrated in particular by the following experiments performed and their results.

According to the invention, the acid-resin-sulfuric acid mixture, as is the case with the sulfuric acid purification of mineral oils, is neutralized in a mixing device, followed by crushing and charring in a semi-coking oven at a semi-coking temperature of 380-400 ° C.

In detail, the course of the experiment was as follows: Starting with acid tar (tar) of the following composition: 500 wt. H2SO4 150 wt. H20 350 wt. free oil and sulfur-bound organic ingredients. 1000 parts by weight.

1) These 1000 parts by weight. tar is now neutralized with 700 parts by weight of CaCO3 according to the following total reaction:

t T

H2SO4 + CaCO3 -> CaSO4 + CC> 2 + H2O + H

(500 parts by weight) (500 parts by weight + \ (680 parts by weight) (thermal effect) 200 parts by weight ICaCOo stoichiom. Excess) 7 ^ (200 parts by weight)

(+ 350 wt. Org. Substances, etc. I tT

+ 150 wt. H, O) J 1 * 1 ° Paln ° - ° s · «20) ^ __ / H2 ° (40 wt.%) 1700 wt.%. tar - »1270 weight. neutral, substance + 430 wt. gaseous effluents. The CLEAR.

Said 1270 parts by weight. the neutralizing agent is not usually storable due to the organic contaminants it contains 7 60573 such as oil, sulfonates, etc.

2) 680 parts by weight obtained from neutralization by semi-coking. CaSO 4 + 200 wt. CaCO 2 - excess.

and + about 70 parts by weight. semi-coke (= about 20% of existing organic matter, namely 350 wt.%).

obtained: 950 wt. to the normal deposit.

These gaseous sulfur products were burned as shown in the second stage of the heat treatment and the solid sulfur residue was subjected to a series of experiments, the performance and results of which are shown below: 1) Extraction of acid tar (solid sulfur product) treated according to the invention

Extraction of the substance was carried out in a bench test using distilled water. Different amounts of extractable material were treated. In this case, a linear relationship could usually be observed during the extraction.

Elution of the substance was carried out at a temperature of 20 ° C to 2 ° C on dry days, with occasional further stirring to ensure complete mixing.

2) Research method

At the end of the experiments, the eluate was filtered. The following analytical values were determined for the filtrate according to the German Standard Method (DEV) for water, wastewater and sludge. The COD determination was performed according to the method of W. Leithe (Die Analyze der Organ. Verunreinigungen in Trink-, Brauch- und Abwässern, page 51).

3) Research results

Extraction amount ................50 g / l 25 g / l 12.5 g / l pH value ................ .. 8.15 8.05 7.85 electricity. conductivity (20) ^ / cm. 2050 1400 .1015 8 60573

Oxidizability mg / l KMnO ^ .... 90.0 51.5 34.0 COD mg / l .................. 91.0 30.2 19.6

Sulphate mg / l SC> 4 ........ 1250 650 600

Chlorides mg / l Cl ........... 6.4 5.7 5.0

Sulphide mg / 1 S ............ no no no display display display

Appearance .................. all samples were clear, free of color and colorless 4) Evaluation of results 4.1. pH The pH is in a weakly basic range. This is due to the negligible solubility of the substances used to neutralize sulfuric acid (eg calcium carbonate).

4.2. Electrical conductivity The electrical conductivity depends on soluble lime salts, in particular calcium sulphate (solubility in the case of semi-coking is expressed as anhydride formation, 0.20 g / 100 g of water, with a slight decrease in solubility with increasing temperature).

4.3. Oxidizability and COD

Oxidation and COD are approximately in the same order of magnitude and show relatively small values that are in part below the extraction values of household waste (oxidizability).

4.4. Sulfate

Sulfate concentrations are typical of gypsum and anhydride extraction. No sulphides could be detected, so that no reduction of sulphate to sulphide takes place at the coking temperature used.

The products obtained as a result of the process according to the invention thus contain harmful substances in the order of magnitude which is clearly below the amount of harmful substances in household waste. The sulphate content of the products is also of the order of magnitude, which is also present in many natural soil constituents, such as clay, loam, etc.

Claims (5)

60573 9 The solid residual products obtained from the treatment of acid tar according to the invention can of course be stored as systematic storage and in admixture with household waste, construction waste, soil and the like and fully comply with the legal regulations for the protection of the environment. 1. Förfaringssätt för att neutralisera och värmebehandla sur tjära, kännetecknat därav, att til tjäran sättes oxider, hydoxy-der eller carbonate av jordalkalier, t.ex. kalk, antingen i torr form or eventuellt i concentrated concentrate wattenuppslamningar, varefter den i halfast or fast form erhällna reaction products, företrädesvis efter sönderdelning, undkastas en Värmebehandling i flera steg, warming en tvä steg, och i det första at 350 ° to below 500 ° C, the medium of which is set up with a gas-containing low-cost product, optionally followed by a mixture of the initial brandy, the above-mentioned, and then the low-cost form of the low-cost product. A process for neutralizing and heat treating acid tar, characterized in that alkali oxides, hydroxides or carbonates, such as lime, in the form of dry or optionally concentrated aqueous slurries are mixed into the tar, followed by a semi-solid solid reaction product, preferably comminuted. in the first stage to a semi-coking treatment at a temperature of 350 ° C to less than 500 ° C, while in the second stage the gaseous semi-coking products, possibly after mixing the initial (start-up) fuel, are burned and finally the solid semi-coke residue is removed from the semi-coking plant. 2. Förfaringssätt enligt patentkravet 1, kännetecknat därav, att jordalkalioxider, -hydroxider, resp. -carbonate for example 11 60573 in the case of a neutralization of the syrup with a risk to the environment, for which the neutralization is negative SC> 2 resp. SO3 is shown as a synergistic solution in the reaction products and above. Process according to Claim 1, characterized in that the alkaline earth oxides, hydroxides or carbonates are used in amounts which exceed the stoichiometric amounts required to neutralize the acids in the subsequent treatment of the reaction products, for example by heating them with negligible low-generation SC 3 and / or SC 3. for neutralization. 3. The method for utilizing the pre-treatment is set out in paragraphs 1 to 2, with the resultant of the use of the neutralization unit (22) in the case of neutralization, for the neutralization medium (21). on the other hand, (31), where applicable, the balance set up an account for neutralization, (23) for blending with the best value under the neutralization procedure, in the case of redundancies (24) for the sale of low-cost neutralization ) with the conclusion (32) for the sale of gas in the form of low-cost products and for the final use of low-cost products, in which case the use of low-cost gas-generating products (26) or in the case of condensation, with the order (29) for the original or initial brand, the same is the same as for the original brand (28) for the original genome to be used in the first instance. Device for carrying out the method according to Claims 1 to 2, characterized in that it has a storage tank for the acid tar (22) to be neutralized, for the neutralizing agent (21) and for any fillers or additives to be added to the neutralizing agent, for example bleaching clay (31). 23) for mixing said ingredients by neutralizing tar, a crushing device (24) for a solid or semi-solid neutralization product, a semi-coking chamber (25) with an air supply device (32) and a gaseous semi-coke product discharge device, and a solid semi-coke residue after or a condensing device in which said exhaust gas is generated and which is optionally further provided with an auxiliary or starting fuel supply device (29) and finally a collecting tank (28) for the solid semi-coke residue extracted from said solid outlet. 4. A claim according to claim 3, which comprises the following provisions (23) at the end of the period of application of the reference form to the dossier body (3), in which case the same neutral means are used, if necessary, and 8) for transport in the field of transport, colors and repair elements, t.ex. en andra skruv (7, 8) en kugghjulskedja el.dyl. it is not attested by a blanding gang. Device according to Claim 3, characterized in that the mixing device (32) has a metering device (3) on the inlet side for mixing the tar neutralizing agent and possibly other additives, a screw mixer (7, 8) on the inlet side for conveying the mixing product and a screw mixer. a cleaning member such as a second screw (7, 8), a gear chain or the like. Device according to Claim 3 or 4, characterized in that a device is provided for forcing the respective reaction vapors and gases through or over the mixing product and in that the dose. The apparatus (3) gives an excess of previously mixed alkaline earth oxides, hydroxides or carbonates or a mixture thereof so that the reaction vapors and gases containing small amounts of sulfuric acid vapor are completely or partially neutralized. 5. The method according to claims 3 or 4, having regard to the application of the invention to the transport of the reaction reaction or resp. -gaseous, genomic or carbonaceous compounds, or a dosage system (3) is incorporated into a mixture of carbon monoxide, helt eller delvis neutraliseras.