DE1645834B2 - PROCESS FOR THE REGENERATION OF USED BLEACHING EARTH FROM OLD RERAFFINATION - Google Patents

Description

The regeneration of used bleaching earth from animal bleaching and cleaning of vegetable and vegetable Oils and Lette and animal bleaching mineral lubricating oils (Erstraflinate) had in the years about ] From 925 to 1935, he was particularly interested. how liii-. can be seen in an extensive literature. O. Kauseh talked about this in »Das Kieselgel und tlic bleaching earths ". Supplementary volume. Springer-Verlag, Jy35. reported in detail. Back then was a major reason for a regeneration the relatively high price of bleaching earth, based on the finished products.

The common material for the production of alkaline bleaching earth are natural raw aluminum silicates Vsie lone. Hentonite. I ullererdc etc. The raw material Ssirtl /. B. dried, classified, broken down to a small grain size, extracted with acid to remove soluble fractions, do CaO. Ic ₂ O ₁ . MgO etc. contain bound, heat us / u dissolve, which creates the actual capillary structure. Mostly ssircl extracted with hydrochloric acid, rarely ion sulfuric acid. After washing with water, thermal activation takes place, ie fin heating aul .VK) up to 300 C. The finished earth contains around 66 ",,, SiO _2. II to IS" / ,, AI, O _{: l} . 3 to 4 "/" IC ₄ O.,. 1 to 3 "," CaO in bound form and still S to H) ¹ V _n H ₂ O water of hydration and is wcil.l At this water content a maximum of blood activity is obtained. According to O. Ekkart (Seifcnsicder- / eitimg. 1931, No. 13, p. 29), the active earths already suffer a noticeable decrease in bleaching activity when the treatment is repeated for longer periods of time. The bleaching earth is mostly used powdery or fine-grained (grain sizes about 300 microns down to 40), for some / wake up. ¹ ii bruised in i orm by sausage or ball · 'i. The inner surface is between 100 and 30Om-Zg and is decisive for the adsorbing activity, which is partly selective because the earth has a slightly or more acidic character. There are many varieties on the market, e.g. Tonsil (Germany), liltrol. Clarsil (LSA.). whereby there are subgroups in every kind, because today you have to fulfill special I ord-Tungen /. B. good Eillrierharkeil and special selectivity, degenüher the state of 1935, the production howling is not only larger and more varied, but also become more rational through modern systems, ie.

In relation to the finished product price, they have become cheaper and better. The Hleicherderegeneraiion today no longer have the meaning as vo ^r 35 years. But where it is still being carried out, there are special cases. In addition, bleaching earth has recently been created by cheap active coals from coal competition; synthetic zeolites have been developed for particularly high requirements (molecular see).

So was z. B. according to OK also in "The silica gel and the bleaching earths", supplementary volume, Springer-Verlag, 1935, p. 93, paragraph 1, used in the regeneration of used fuller's earth from the initial refining as a solvent in soda and table salt, which was used to boil the earth in an autoclave, which separated oil and left a rope-like broth. This was then neutralized with sulfuric acid, in the presence of the earth, to separate the fatty acid from the soap. When the earth was later reactivated, one with 8 to 10 ⁿ / _n carbon was obtained, that is to say, an active carbon was practically produced.

According to US Pat. No. 1,132,054, used fuller's earth was used for regeneration these cooked with acid. When using such processes on fuller's earth from the two-part refining one would not come to a success.

In the second refining of waste oils, we have for the time being

Processes that no longer require fuller's earth.

no entry found yet. Renewable waste oils

4 »are mainly engine oils, about two thirds of which come from the carburetor engine and one third from the diesel engine. In addition, machine oils are also regenerated to a lesser extent. It is characteristic of modern engine oils that they are all "alloyed". ie, have 5 to 7 "Z obtain _n additives without would not be possible, the high power of the motors. The most important additives sine ¹ z. B. Oil-soluble sulfonates of calcium and barium which sediments hold (carbon black and fine abrasion) in floats (so-called Detergents), zinc alkyldithio phosphates, which are corrosion and oxidation inhibitors, and viscosity improvers such as polymethacrylic acid esters and polyisobutene, depending on the temperature behavior of the lubricating oil

Γ, Γ) improve. Some of the additives are found in the waste oil sets again, partly decomposed, and besides, it is durcl a stronger soot deposit, discolored deep black. The soot is so fine that it is not filtered off In addition, cleaning agents such as gasoline, diesel oil and trichlorethylene etc. get into the waste oil. Dc The water content is usually around 1 () "/".

In the second refining, water is first used with a pre-distillation. Gasoline, trichlorethylene, etc. separated (up to about 160 C). From the hot, water

^S 5 free black residue settles in the interim storage, noticeable amounts of sediment (mechanical abrasion, dirt). This is followed by refining with 96 ⁿ / _n sulfuric acid, which is 30%

I 645 834

4ii ι Mirziinehnien is. The more recent earth has been used up a little less

| v _u | ii L'.erk in a container (with Spiizl -.onus inside) Siiuivteer, could get more from Lö-.ung

j, ..ιΐ ...- iiei. you need about 5% sehwe- adsorb and have a temperature of 30 ° C

jei .. hi '-. With a metering pump for oil and a stronger decomposing effect on the additives, in any case

fi! .- i 'IiΉ' Schwelelsaure over a mixed stretch; ". will l.idalkalisulfonalc. ^ - split. Sulfuric acid

j-i μ Ih-Hl-i. Is the utilization of sulfuric acid decomposed in a reducing manner. but before illem the zinc-alkyl

i-. · ■■ - ■: "niaii gets by with about 3" / ". but drives diihiophosphate destroyed, the unier ILS- / clumping,

i-l - :: l.iiK in a pickling tank. For the separation see oletin cleavage, zinc phosphate formation disintegrates. the end

i!., saiiiehaiz or acid void, a thick, tenacious SO._, and ILS enisiehi sulfur, the üas condensa '.

! Si .. ·. which is peeled off after 12 to 24 hours, m milky iärbl.

1 ". , '-aiircieer contains about K) ",, free sulfuric acid, so it is no wonder that Z.'

I:. .!. 'imgsprodukie with Alibauslopen from the oil, with today's conditions with the used oil (before

S. ''. ·: ■■■ '-on lead, calcium. Barium, iron, zinc. eivva 6 years the additive content of the same nkhl

, - ,: ... iiiiuni etc. and also the soot. The pipe - once half as high as yelts. L) it is hopeless

..;., .. H is colored dark brown because it contains 15 space to regenerate the used earth. Man i-i

1.1, ;; i!,. i.si. suspended acid tar is found, which predominantly thinks that the adsofnated and

i '· ■ -vi. and there are also residual absorbed substances and decomposition products that have remained in solution

Ii iLMi of the additives present. With the refining of the oil and the sulphates the capillary system of the earth

ν ι block a small part of the sulfuric acid in a reducing

I : <: ..ι S () _.- Education decomposes, a part of which can be made impossible to revitalize the earth. It is also

1 ui..em ventilator above the reactor can be seen that the difference in the contamination

Y. ■■■■■■ the fuller's earth in contrast to the waste earth

! : iiht two ways of further processing. When bleaching real oils and Latvian and mineral

j,! ·, 11 is the acid oil in a heated stirring oils,. '. B. of the IL. steam cylinder oil (see B. Il a s-

I.-i-i'-T transferred, heated to 100 to 110 C, 25 is, Seifensiederzeitung, 1930, No. 41. P. 722 bis

ι - ..: / uersi with 5'V ₁₁ powdery fuller's earth intensive 724), is very large and of a completely different kind.

\ eiv'i'-rt. with still some SO ₂ for suction. So the question of the possibility of one depends

jib; · ..; ■ iebLii wire. After about 20 minutes, the used oil bleaching earth will be used to regenerate it ah whether it

New;' ! isation about '.'., Gewichisprozeni hydrated lime isl possible, the capillary rupture of the earth again

/ iigc-izt. to make that with the remaining SOo calcium sulfite 30 or not.

Hili .. ·: and some with r Teichbarer Hoso ₁ Eradicating used F.rde may be because

tiip ·. As soon as the oil-earth mixture is neutral (according to the oil content by burning, if

fi, '· .: 10 to 15 minutes), gets hot on a filter - it is possible. add them to the garbage, for example.

«■ ι; -ι- gone from which the raffinate is clear and from Is it burned for itself, what no one howls

■! I.iur paint runs out. The filled press becomes 35 more, an expensive dust separation is necessary because

\ lj used earth in F'oim of a relatively solid the F.rde a lot of fly ash lie.eu.

Ki.ehen spread. It's jet black and the most common disposal is an approved one

viiiL-n oil content around 50 Gcv.ichtspiozent. Landfill, as there is hardly any soil in the water storage

ilci of the newer method is like above in the oil dispenses. Nevertheless, it turns out that with long-

W., nre pre-bleached with fuller's earth. after about 3 years of storage the earth gives off oil, one

wic'itsp: ozent. but no hydrated lime added. The groundwater carving causes why the

The constantly stirred mixture is then practically destroyed by a water supervisory authority.

Special pump (because of the erosion) has a heat source.

taiis.-heating with about 300 C in a vacuum heat a bleaching earth regeneration supplied to a distillation column to cover costs. With the following 45 feasible, a more than 90 "" Wicder-Vakiium-steam distillation would have to be carried out, activation would be achieved and the by-products that in the bottom of the column the lubricating oil like oil and salts would have to have a viscosity somewhat determined in terms of value There is also the bleaching process. Not only would a chemically viable earth be included, while a distillate would have to be found as a forerun (perhaps a way, but also a diesel oil) and a spindle oil fraction hot swamp product with the bleaching earth ki th and modern equipment. On the other hand, it may be drawn off via a template and come out after a ke.ne luxury plant, because the intermediate layer is promoted, in which there are and will be vveitcigcrühit medium-sized Zwcitrafüncure plants around 100 C the oil - only the big ones maybe buy a plant - soil mix on a semi-automatic filter press The smaller ones may be pumped into the neighborhood where a lighter oil can now be drawn from the earth. Another limitation is that no publishing house is separated. If the press is full, the wastewater problem is cured, and no air or steam can be briefly blown out and the press may be cleaned,
then emptied. The present invention therefore relates to a method for making the earth deep black again and containing 30 to 35% of the weight of used fuller's earth. It should be added that when refining through oil extraction with solvents, the sour oil is usually 48 hours acid extraction of the deoiled earth (similar to the interim storage!

The older earth has absorbed more acid tar, washed out earth, characterized in that

contains about 10 ⁿ / ₀ hydrated lime, the soot in acid tar 65

and adsorbed additive or replacement product a) the waste crude from a short-term extraction with

of that. Part of the free sulfuric acid has a share in the aromatic gasoline hydrocarbon

; .. ilk plaster formed. Subjected to 10 to 45 ^° C. or in one order

645

5 to 10 ('lower temperature rich with halogenating K oh Ic η u assersiolleii. In particular i nchloräihs len, extracted w ^: vd. Whereby a lighter color is recovered, which corresponds to the Rcraflinul on Oualital.;,

h | after drying, it is subjected to a mixed post-treatment in the heat / wipe at about 170 to 350 ° C ,

c) the bleaching earth treated in this way from an extraction with dilute hydrochloric acid, nitric acid or other suitable acids, subjected to a thermal aftertreatment after washing out is subjected.

The following experiments on a laboratory scale are intended to explain the invention in more detail.

1. The extraction of the oleaginous waste oil bleaching earth with solvents

ZO

Comparative experiment 1

Extraction of the calcareous fuller's earth with a mixture of benzene and normal benzine (rich in heptane) 3: 7. Boiling range around 85 "C.

100 g of earth were boiled with 400 ml of solvent in a 1 l glass flask with a reflux condenser for 30 minutes. Then wi.p.le the earth on a suction filter at 60 to 70 C, washed a little with warm solvent, vacuum the cake as dry as possible under anti-back and put to dry in the drying cabinet with the temperature increasing from 100 to 140 C. The solvent was removed from the brown filtrate by distillation. A brown oil was obtained. Yield; ^; S percent by weight, viscosity 6.5 Engler at 50C.

The oil could be sold as heating oil (at a low price), better as the soaked waste oil before refining to be returned (ballast, but not lost).

Attempt L

Potash extraction of the same soil with white spirit (\> 5 hi, 140 C boiling range). Aroma content about I (> ". '". Simultaneous experiment with Shell specialty gasoline (100 to 125 '-R) with 3.5 ", aromatics. The 4s both extractions twist like experiment I duichfefüiirl. ir'.r was at about 25 C in the l-i beaker With a stirrer, the soil is intensely cooked for 10 minutes. Every earth was back on the nutsche lall sucked off, with cold solvent a little lia> washed. The pressed two filter cakes V. were dried in the drying cabinet. ! 11 both 1: il! '.' Ii w; .i "but the I illral came out light yellow. After the abortion de. The same yellow lubricating oil was obtained back in both solvents. The oil was slightly cracked, the smell could be determined, which for the slightly darker one Stab was the cause. Yield 37 percent by weight based on input. Viscosity 6.5 ° E at 50 C.

Result: This method of cold extraction proved (m that an oil equivalent to Kcrafii'iat can be recovered. O. Hassel (Seifensieder-Zeitung, 1930, No. 41, pp. 722 to 724) had bleaching earth (I ullererde. and Eiltrol) from the bleaching of real oils and fats and Icißdanipfzylindcröl extracted hot with completely aromatic gasoline and also obtained light extract. He expressly emphasizes that this result is only possible with the aromatic oil lien / in cr / ielhai. Real (lic nm \ IaIu are dissolvable \ iel \ isk> ser than foul oil, the t \ i \ r (O! At 50 C hall. The ilcil'.ilainpl / v linderöl 11 c _; j 1 on the other hand in the viscosity about ten times as high and is a viscous mass at Raumiempeiaiurlast at the lock point. The call action would be uneconomical in some cases because it takes too long and requires too much solvent. That the cold extraction of the waste oil bleaching earth was successful, i-.l surprisingly and is related to the fact that the solution is so windy wedge of the thin oil in cold gasoline is greater than that of the acid resin. It is also essential for the technology that there was no difference in the light portion of the extract between Ί estbenzin and special benzine with their different aromatic content. B. Heptane, the clv ,! 5 times as expensive can be used.

Attempt 2

Cold extraction of said soil with trichlorethylene. The experiment was carried out in the same way as (2) carried out. At an extraction temperature of 25 ° C., the oil obtained was light brown. Was the at 15 C. Repeated extraction, made the oil lighter. That However, the product can still be used as a lubricating oil because not all oils have to be that light.

However, with experiment 2 it was ensured that a Normally valued light oil can be recovered, which the reraflinate in larbe and viscosity corresponds. Here -uicli is the E. extraction time to be assessed as favorable from a procedural point of view.

2. Extraction of the oil-free soil with hot 20 "," iger hydrochloric acid

Experiment 3: Extraction of the soil from experiment 2 with a reactivation experiment

50g of the black powdery mass was mixed with the 4faclien Volume 20 _"; ,, hydrochloric acid heated iinltr constant stirring in a glass beaker and held for about 10 minutes at 70 to 90 C After that something was allowed to cool and the Iirde on the suction filter with acid-resistant I ilter. abliliert and soak with hot distilled water.The ililtate had turned yellowish, which was mainly due to dissolved iron.

The jelly cake had become a little lighter. I 1 was in a l'orzellanschale in dry chrama, dried at ILU C. After drying it was the bowl with the earth pushed into a muffle furnace set at 700 ° C. Since this showed that the black substance burned off on the earth, was waited until the earth had just turned white. It was feared that the earth had been burned to death.

This had to be shown by the bleaching experiment with Spindle Oil Saucröl. The sour oil was _{intensely bleached with 3 "/ 0} regenerated earth and 1" / "hydrated lime at 10OC, which took about 5 minutes. It was then filtered hot on the suction filter. The earth had turned black again and the volute was light. Determination of the color number according to ASTM

gave the value 1.5 to 2. Amazingly, the bleaching effect of the fresh earth was practically achieved.

Now this used earth was extracted again cold and dried, subjected again to the hydrochloric acid extraction, as dried and before burned down in the muffle furnace and carried out the bleaching test again after cooling. Also this time it was the earth was black and the ASTM color number was again in the range of 1.5 to 2. The bleaching power of the earth so had not been significantly damaged.

Comment: The result of these experiments is very surprising, because it proves that a capillary blockage in the bleaching earth by sulfates and other arrears did not occur. The acid tar contains much more of the spindle oil free sulfuric acid (about double) than is the case with lubricating oil. The hydrochloric acid must also Acid tar components, e.g. B. sulfonic acid, with dissolved out. Calcium sulfate when it arose was hence probably on the surface of the bleaching earth particles in a form harmless to the bleaching.

3. The operational process elaboration 1. Gasoline cold extraction

This does not cause the designer any particular difficulties. So you can z. B. with two KaItextraktions-Rührbchäkern one or two automatic filter presses, wash the earth with recovered solvent, with steam

ίο blow out. Since you are in the filter press in countercurrent When washing out (this is its advantage), almost pure oil is pushed out first, before a more dilute solution follows. So you get by with relatively little detergent. If the oil solution is aiif in an intermediate tank taken, you can use the level regulator auto matically feed a distillation, the solvent and oil separates from each other. The hydrous Steam condensate goes through an automatic separator that separates gasoline from water. Ls would be in With the heated filter press it is even possible to dry the earth with inert gas (flue gas).

Experiment 4: Extraction of an extracted soil from the diligent contact bleaching with hot hydrochloric acid and subsequent reactivation

The soil sample was taken from the facility where it was attached to the Niagara semi-automatic filter press almost powdery because it was blown out with steam. It contains around 33 per cent. Oil. Even in this case the cold extraction gave a light oil. (These oils are consistently lighter than the ones after the older way of working.) The soil is jet black, even after solvent extraction. During the hydrochloric acid extraction, it was noticeable that the filtrate was replaced by iron was colored more yellow. But this is not surprising, because the earth in the plant on the way from Bleaching tank via the pump to the vacuum column and on to the storage tank and the filter press It causes erosion in the pipes and therefore more iron is found. Activation in the muffle furnace again showed almost the activity of the fresh earth. But it "seems to be the case that the hot contact earth is easier to regenerate than the heavily calcareous one.

The feared blocking of the adsorbent Capillary spaces in the fuller's earth are present in both cases did not occur. Of course, in the case of the calcareous earth, sulfuric acid cannot be used for extraction will.

Since the hot contact bleaching today at the two refineries is predominant. all have their own wastewater treatment plants in which residual emulsions are to be split, for which both iron chloride and calcium chloride are used (iron chloride is mostly too expensive, ferrous sulphate is for that. technically, cheaper), a concentrated solution of these salts can be used in-house after a certain amount of pre-cleaning or in the neighboring use. Then these solutions are no longer worthless because they reduce the purchase of these reagents or make them unnecessary. Ferric chloride is More valuable than calcium chloride in this application because its hydroxide flake is a good oil absorber is.

Compared to other extraction acids, e.g. B. Nitric acid, the hydrochloric acid is priced and abfallm :: ßi2 frankly most beneficial.

2. The hydrochloric acid extraction

Even this no longer presents any particular difficulties in terms of corrosion technology. So can he Extraction tanks are clad in titanium, while the pipes are made of plastic (polyethylene, PVC etc.). Even the filter press is now available with a plastic clad with a plastic frame and plastic filter cloths. Since you are here in the If countercurrent works, you can collect the first concentrated, low-acid runoff separately and feed back the thinner acid before replenishing with fresh acid. Only very dilute acidic wastewater may be drained into the sewage system after neutralization.

3. Drying and reactivating the fuller's earth

This is the most difficult operation in technical operations, as it has to be carried out with precisely controlled temperature and dwell time in the furnace. Naturally, you cannot use 700 ° C for this as in the laboratory, but have to work in a temperature range of around 400 to 500 ° C. For some years now, however, the so-called fluidized bed reactor, an Accregat, has been available for this purpose. in which the granular or pound-like mass is to be kept in suspension and constant mixing above a sieve bottom by means of a flowing hot gas stream. that no better temperature ineffectiveness is possible. In the present case, the heating gas (flue gas) must have so much oxygen overflow that the soot is burned off on the bleaching earth.

Small-scale tests have shown that it is also advantageous. carry out the oxidative batch of fuller's earth at about 170 to 3r'0 ^: C directly r, ac of the oil extraction and then let the hydrochloric acid extraction with washing and drying follow ζ. In the technical fluidized bed reactor, a gray earth was obtained, which therefore still contains small amounts of carbon (below Γ ¹ “). When smoking after the hydrochloric acid extraction, the result was that the earth was about half its size

ίο

Has lost its daily iron and lime content: that new capillary spaces have been created and that

Instead of 4% iron, they only contain 2 ⁿ / ₀ .

It was further ascertained that the bleaching activity of these was moderate on the inner surface of the bleaching earth

activated soil was certainly higher than the active carbon particles

ler fresh soil. The explanation is seen therein. 5 is gentle.

Claims (1)

645 834 Claim: \ experienced for the regeneration of used bleaching earth from the waste oil reraflinaliun by oil extraction with solvents. Acid exirakiion of the de-oiled Lide (similar to the creation of Erischerde) and gentle burning of the washed-out lid, d a d u r c h g e k e η η ζ e i c Ii η e ι. since 1.1 al the Ahfallerde a short-term extraction mil a ro ma le η arme η petrol kohl en water open at IO up to 45 C or in a temperature range lower by 5 to Kl C with halogenated hydrocarbons, in particular trichlorethylene, is extracted, a light-colored extract being recovered that corresponds to the quality of the rcraffinate, b) after pre-drying a thermal aftertreatment in a fluidized bed furnace between approx Is subjected to 170 to 350 C, c) the bleaching earth treated in this way from an extraction with dilute hydrochloric acid, nitric acid or other suitable acids and subjected is subjected to a thermal aftertreatment after washing.