DE2007456A1 - Production and isolation of lower aliphatic acids - Google Patents

Description

Production and isolation of lower aliphatic acids

The invention relates to the production of carboxylic acids and especially to the production of lower ones
aliphatic acids by reacting carbon monoxide with an olefin and water in the presence of a catalyst.
The invention particularly relates to improvements in
Catalyst compositions for such synthesis, and improvements on ancestors using such catalyst compositions. The invention also relates to the isolation of the carboxylic acid produced from a mixture with sulfuric acid, water and olefin sulfonation products.

The reaction of an olefin, ζ, B ₀ of propylene, with carbon monoxide in the presence of highly concentrated (90 % or
above) sulfuric acid as a catalyst and subsequent
Dilution and reaction with water to terminate
Synthesis of organic acid is in the USA deed

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2,831,877. The first stage of the reaction is carried out under pressure at moderate temperature. In US Pat. No. 3,053,869, a similar process is described in which the catalyst used is a spent alkylating acid with a titratable H ^ SO, apparatus content of 79 to 90% by weight. In the patent specification it is stated that this used alkylating acid contains 80 to 90% E, SO, "based on the total titratable acidity, and only 1 to b ^c h water, while the Ivest from" red oils ", which are complex mixtures of polyolefins, organic sulfates and sulfonates.

In the patents mentioned, the need for a "high H ^ SO. concentration in the catalyst, as well as one emphasizes low water content. In the USA patent specification 2,876,241, however, the difficulties are also described when using high concentration sulfuric acid aLs Catalyst for the synthesis of the organic acid occur.

In order to end the proceedings, it is necessary to be perpetrators. txic; To add quantities of water, after which the bulk of this'., Vissers rcu3 are removed in order to concentrate the sulfuric acid again for recycling as a catalyst. Hydroxyalkyl sulfonic acids are difficult to remove from sulfuric acid separate, and it was found that in certain sections of the concentration by evaporation of these acids Charring and tar formation lead to the development of SO ^. Instead of re-concentrating the sulfuric acid catalyst a more expensive acid regeneration by evaporation was therefore considered, or the use of Substitute catalysts, such as those in the aforementioned U.S. patent 2,876,241 described acid mixtures are preferred.

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BATH ORIGINAL

US Pat. No. 3,282,973 describes the use of organic sulfonic acids as catalysts for the same reactions, namely of olefins with OO and JnGdiir, for the production of organic acids. The ones mentioned in this patent Catalysts differ from the catalysts according to the invention decisively in that the sulfonic acid is a hydroxoxyalkylsulfonic acid or a mixture thereof with its sulfuric acid ester, which is expediently derived from the product of the sulfonation. Olefins can exist, as it is used for the production of carlo-acid. Biner der Suifonsaurekataiyuotor,:. According to the USA patent 3 28 <? 973, on the other hand, consists of alcoholsulphonic acid produced by sulphonation of paraffins. A major advantage of the inventive catalyst compared to the catalysts known from the USA patent specification 3,282,973 is that it contains, aie Hydrox yalkylsulphonic acid and its sulfuric acid ester, u ± e constituents of the catalyst of the invention, n ". the catalyst is to be used:

Thus, in a continuous process sur Zr-seugvxng the carboxylic acid, in the; the catalyst is recycled in aae 7 ^ / - faliren A ^ ird, aie Oleiinsulfonierungaprcau. ·: ^ - ?, which are essential "components" of the inventive catalyst are produced in the process in α en; the catalyst is circulated. can this continuous process can proceed without daii it is necessary OlefinsulfonierungsproQukte lost the ir ;. method nachzufüi.en go _s the Srgängung of Kataj-ysatorverlusten by simply adding Sc.v .- -. ei.'3lsäure happen those with the olefin reactant below

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Formation of the sulfonation reacts. This addition In thorn required dimensions is usually made in go small Kengen that the addition of the catalyst composition: in: ense t ^ ung not changed significantly as the continuous process proceeds.

The separation of the carboxylic acid produced and of '// anner from the product mixture by distillation is mentioned in US Pat. No. 2,876,241. In this patent, the difficulty of recovering the concentrated S _c hwefelöäurekatalysators is explained and cause the reconcentration ues sulfuric acid catalyst by vaporization because of the presence of hydroxyalkanesulfonic acids, the char and tar formation under sulfur dioxide development, exceptionally referred to as difficult or impossible from the same patent specification it can be seen inter alia · - s-att a re-concentration of the acid by evaporation a complete regeneration of the sulfuric acid is necessary. The patent specification then proposes the use of additional catalysts in order to avoid the difficulties in distilling the product mixture which contains sulfuric acid.

Surprisingly, a method of manufacture has now been found of aliphatic olefins and carboxylic acids by reacting CO with water in the presence of a catalyst composition found, which is characterized in that a catalyst composition is used which 15 to 90 wt .-; £ hydroxyalkanesulfonic acid and mixtures thereof with its sulfuric acid ester, 0 to 75 wt .-> 6 H ^ SO. and nichu contains more than 20% by weight v / water. The invention also enables lower aliphatic acid to be separated off and from V / ater from a product mixture that

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components and also sulfuric acid, a hydroxyalkanesulfonic acid and contains its sulfuric acid ester, solved by the fact that the product mixture is distilled under reduced pressure until practically all in the Product mixture containing lower aliphatic ^ acid is distilled off from the product mixture. So in one respect the invention relates to use a new catalyst composition for the production of ■ an aliphatic, organic acid, made up of an aliphatic olefin and carbon monoxide, while in others Respect the separation of lower aliphatic acid and of water from a product mixture that contains these ingredients and also sulfuric acid, a hydroxyalkanesulfonic acid and contains its sulfuric acid ester. However, these various measures can result in an overall procedure for the production and isolation of a lower aliphatic acid are combined, the batchwise or can be carried out continuously, in one embodiment of the invention, in which the two inventive features are combined, is (a) carbon monoxide with a lower aliphatic olefin in a reaction zone in the presence of a catalyst, the HpSO. contains, implemented, (b) the product mixture from the reaction zone with Water added, aliphatic acid and water from the Product mixture from stage Cb) distilled off, the distillation at a pressure of less than 300 mm Hg performed absolutely and at a temperature of less than 200 "C. until practically all of the resulting aliphatic Acid is distilled over and the water is less .Is

20% by weight of the still residue, and the steps (a), (b) and (e) defined above using the distillation residue from step (c) as a catalyst repeated in the next stage (a) »

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Aliphatic ΰ-efins which are suitable for aas inventive concept: \\ "are propylene, butene, pentori, witcher :, ileptene and octene. In general wera ^ r. ? - ± e _c ; cr.ar.ri :: e .. fine preferred, since other olefins offer one or r .-. Honors α er: "the following difficulties: slow implementation :,. ·.;. .-. Bad Yield, formation of a complex mixture of isomeric acids, polymerization and formation of ionic residues which are less active when circulated.

The olefin can be fed to the reaction in a ^ o? Ileriv / as:; exp "t.offmixture, which changes up to 50 or 60 "ρ; f important Koiilenwasserstcffe and outer ^ Ieic ^ e ;, has. A typical source of propylene may be, for example, a propylene-rich stream from a; pe tr ocher.;! see processes or from a., petroleum or Zrn ^ asreini ^ drive, which can also, ".

In addition to carbon monoxide, formic acid can be used in the reaction should be used as this acid changes itself on contact with concentrated sulfuric acid to form pure:., Decomposes carbon monoxide and water.

Brfindungsgen-äß v / ird in the described carbons: "urosynthesis a catalyst is used which contains considerable amounts of olefin sulfonation products, i.e. hydroxylsulfonic acid and its sulfuric acid ester, either alone or preferably in a catalyst mixture, aie except -c ::. Contains sulfuric acid.

In the manufacture of Ioobut.ters? 'Iure from propylene ontst ^ ht TxIs by-product by su fonation of the

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for example if-hydroxypropane-1-sulfonic acid:

Oh (HSA)

which is the product of the sulfonation of 1 mole of propylene with 1 KoI represents sulfuric acid. Another propylene sulfonation by-product is the sulfuric acid ester, des erjaen By-product:. ·

CH _x -CH-CHy-SO _x H

OSO _x H. "'(SAE),

which represents the condensation product of hydroxypropanesulfonic acid with a further mole of sulfuric acid. The first sulfonation product described above is abbreviated in the following n-.it HSA and the second product is abbreviated to SAE. In catalyst mixtures with sulfuric these two sulfonation are adjacent in the catalyst mixture irn öi.eieiigewicht ago · The relative concentration of beiaen products at equilibrium depends on several variables, including the SchA ^ efelsäurekonzentration in Kutali'- sator mixture, the concentration of having in Kischung the water present in the catalyst, the temperature of the mixture and other factors which can change during the circulation and recycling of the catalyst through the reaction zones and the product recovery zones. Generally <k - AEL · be noted that in the high pressure reaction zone, the ixleichgewiejat to higher concentration of SAE, and aar. Zones in which the catalyst is present with higher concentrations of 'barrel, the equilibrium tends towards higher concentrations of HSA. One for the inventions similar, 3e »- ^"

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Purposes suitable catalyst composition consists of about 15 to 100 wt .- # Olefinsulfonierungsprodukten, 0 to about Ib wt .-% H ^ SO, and usually about 5 to 20 wt. -Fo and preferably no more than about 30 wt ° p Water. When the catalyst is in a continuous. Ion process is circulated, small amounts of various organic by-products can form in the catalyst fed in, but these seldom make up more than about 15 ⁰ A of the mixture. All of the above amounts are given in terms of weight percent of the catalyst as it is introduced into the reaction vessel.

At the start of a batch process using the catalyst in which CO with olefin and If water is reacted in the presence of a catalyst, it is expedient to first feed the catalyst into the reactor, which may contain water, and then to supply CO to bring the pressure to the operating value. After the catalyst is saturated with CO and the The temperature and pressure are adjusted to the chosen reaction conditions, the olefin feed slowly becomes supplied, and CO added to the extent necessary to maintain the pressure. Towards the end of the reaction, the pressure in the reactor stabilizes without the addition of CO being necessary. then the reactor is cooled, the pressure is released and water can be added. Further information can be found in this section V / ater may be required to synthesize the organic Terminate acid if insufficient in the pressure reactor. Amount of water was available. You can also use water add. to the 'product stream for a more efficient distillation to dilute.

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:. - 9'- 20σ7Α56

In the. Implementation of the method according to the invention contains the catalyst fed to the reactor considerable proportion of olefin sulfonation products. In particularly preferred embodiments, the contains Catalyst also has a proportion of H ^ SO..In most of them In some cases the catalyst mixture contains some water and usually some organic products (e.g. Polymers, various organic acids and esters, etc.). Particularly preferred 'catalysts have compositions within the following ranges, given in wt. ~ fo of the catalyst fed to the reactor.

Olefin sulfonation products
'(e.g. HSA and SAE) "15 - 90%

H ₂ SO ₄ 10 - 75%

Water . - 5 - 20 Y ₀

Various organic substances 0 - 15 f °

Pure olefin 00-reaction in the pressure vessel at a temperature in the range of usually 50 - 1 00 ^W C preferred, but the method can also at other temperatures in the range of about 10 to about 150 are performed ^v 0th In the most preferred embodiments, the pressure in the reactor is in the range of 210-560 atmospheres (3000-8000 psig). However, the process can be performed at other pressures over a broader range of from about 35 to about 1000 atmospheres (500-15,000 psig).

The ratio of QlefinbeSchickung to Katalysatorbe- "scriickung for the reaction zone may vary within a wide: up etv» ^r a 1 2 100 indicated Bem.chs of about 1 J 5 as the ratio of Gewiclrttailen 0.'af inbeschickung au catalysis

0 0 983772224

Sator charging with exclusion of water, chosen weraei ,. In order to achieve optimal operating results, it is usual a ratio in the range of about 1:10 to about 1:40 parts by weight of olefin to catalyst is preferred.

Then, the product mixture from the reaction zone is removed and can be displaced as required sser V / _a, uil to reduce decomposition of the organic substances in the anachliesiienden separation. For this purpose, about 1 part v / water per 3 to 7 parts by weight of sulfuric acid is appropriate in the mixture. The product mixture now consists of the carboxylic acid produced, water and catalyst mixture, including olefin sulfonation products, ie hydroxyalkanesulfonic acid and its sulfuric acid ester, as well as sulfuric acid. Even if the initial catalyst feed to the reactor consists of concentrated H 2 SO-, as may be useful at the start of a continuous process, certain amounts of olefin sulfonation products will be formed in the reactor and these will be in the first product mixture which is the separation and contained in the first recovered catalyst, which is recycled to a reactor.

When the product is sufficiently diluted, the mixture is vacuum distilled, usually in the range of about 10 to about 50 mm Hg, but in some embodiments up to about 300 mm Hg. In such reduced pressures the Garbonsäureprodukt can together with a part of the V / ater are distilled off at temperatures never 'DOO ^u G exceed and thus are _(temperature below the Zersetzung-, would take place at a considerable decomposition of the sulfonation products. The dwell time, can be achieved by applying thin film distillation or

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other high-performance distillation processes will. The optional use of an inert gas flow (e.g. nitrogen) for stripping, also supports the separation of the product.

During the separation, it is advantageous to use steam in countercurrent apply, which provides the necessary heat and. Leads product vapors to the condensing equipment. This steam stripping offers an additional benefit Means for precise control of the distillation column to to facilitate complete separation of the carboxylic acid product in a single pass. The remaining Mixture of sulfuric acid and sulfonation products with stiff water can either be used directly as a catalyst returned or, if necessary, before repatriation to a second thin-film evaporator further concentrated will.

example 1

Production of isobutyric acid by reacting C O with propylene and water in a batch operation

Various attempts are made with catalyst compositions, Catalyst and olefin feeds and heat conditions as set out in Table I for the experiments in question. With everyone Try the catalyst in the specified amount introduced into a shaking autoclave lined with 2antalum with a nominal volume of 300 ecm. Then it will be the catalyst to the specified reaction temperature warmed up. The vessel is rinsed several times with CO and then brought to the pressure given in Table I with CO.

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The autoclave is shaken for one hour in order to saturate the catalyst with .CO. Liquid propylene is then introduced into the reactor for a long time by pumping it in at a rate of 1 to 2 ml per minute. CO is supplied as necessary to keep the pressure: In dec Gef ^: .ii3 within the given range. ~.! An addition of CO e.nn the pressure has stabilized, without there (3 is required, the .Autoklav is cooled and depressurized.

The one removed from the autoclave is removed with each attempt

diluted with water so that the diluted Ki se hung about 1 part V / aaser 3 to 4 parts IL, S Ο *, contains. The distillation apparatus consists of a O) O sr.i Pyrexdestillationskolben which is üiriftiiv provided with a stirrer, glass tube to introduce a stream of nitrogen "and a Dampfauolaß. The flask is placed in a heating jacket, with which the heat required for the distillation is supplied. 200 ml of the diluted mixture are added to the distillation flask and the D; ^ mpf aus laß is connected to a cooler which is connected to a vacuum pump at the same time. After the pressure in αem system at 10 mm Hg is lowered, the temperature of the liquid in the flask was rapidly raised to 140 "C. The total heating time is 9 Hinuten. In jeuem? Ull be jo f * isobutyric acid recovered. The Proaukuauobeuten and uie Analysis values for the recovered catalyst for the various experiments are listed in Table I.

The experiments 1, 2 and 3 show the execution,, sform major. i, _r finaung, aie to the isolation of generated carboxylic acid üun a mixture thereof with ucnwo.i'olaüure, ".. 'aa.ifi. · relates una Olefinsulfonierungsprodukten. Verüucri 1 bieget almost optimal conditions for the environmental

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Settlement using concentrated ILJSO as a catalyst. Under these conditions, the ^J rocuk'curnsatz, based on the olefin used, is 92% with only 7 "A conversion to'HSA and SAE.- The experiments 2 and 3" explain changes in the product conversion and in the olefin sulfonation, -die through higher olefin to catalyst ratios and higher reaction temperatures. The catalyst recovered in all of these experiments can be returned to the reactor for further use as a catalyst for subsequent experiments. Experiments 4 to 7 illustrate embodiments of the invention in which the two inventive features of the catalyst composition of oxider carboxylic acid recovery are combined.

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Table I.

Catalyst composition (weight reactor charge (G)

attempt

(Comp.)

(Comp.)

ο 3 (Comp.)
ο

92.3
92.3
92.3
46.3
44.3
44.3

H ^ O

7.7 7.7 7.7 10.4 6.0 6.0 6.9

HSA

19.7 11.5 11.5 92.3

catalyst Propylene 225 ' 16 187 42 214 • 32 169 6.4 179 7.0 200 7.9 210 10.5

HSA - 2-hydroxypropane-1-sulfonic acid SAE - conosulfate ester from HSA

Tab. Ol ie I (? Öi ts

KJ KJ K)

attempt Reaction conditions
"C atU. (Pivifr) '.' (ΐβσο) . Conversion of propylene
to isobutyric acid,
95 given catalyst
(Weight-fj)
• H ^ SO ₄ H ^ O H3A 6.3 1.4 SAE 112 (1700) 91.5 10.4 6.5 0.5 ■ '"" 50 / 120 (1,600) 92 75 * 5 4.7 i1-, 7 " 7.2 50 112. (4000) 74 67.5 9.2 ■ 20.0 ' 15.6 A ' (Comp' * ■ '). · ■ '1.00 281 ., (4000) ■ 47 48.0 6.5 16.1 21.5 2 (Comp.) 75 281 (5500) / V,; '', -64 44.5 5.7 17.3 ' 32.6 3 (Comp.) 75. 387 (3000) ■■ 61 46.8 5.8 94.0 29.7 4th .75 211 75 5 ■ .70- : 28. 6th 7th

CJl CD

- 16 Example 2

A continuous process according to the invention is carried out as follows:

100 parts by weight of propylene} 70 parts by weight of carbon monoxide and 19 ^ -0 parts by weight of cycle catalyst were continuously introduced into a high-pressure reaction vessel. The contents of the vessel are moved and the. If necessary, the contents can be cooled in order to maintain the desired temperature value of 55 "C. The reactor pressure is kept at 550 atm GO% by weight of propylene sulfonation products. A feed stream of 170 parts by weight of sulfuric acid and 37 parts by weight of water is also introduced into the reactor. Contains isobutyric acid The product stream is diluted with 238 Gewichtsteiien water to the decomposition tendency of the isobutyric acid and the SuIfonsäurebestandteile reduce the diluted product stream is continuously in a two-stage distillation system for the isolation of ^{isobutyric;..} I.ure introduced una recovering catalyst.

The first stage of the distillation system is as follows built Γ

Σίι. Glass tube; cä i. a length of 25 cm and a diameter of ':: .-; he vo: » '<:. , j or-i \ n rd clamped vertically. The obure end of the hoxirn v / iru is connected to a cooler, which in turn is connected to a vacuum pump. Close to the upper * Zr.-ia befir .-. Xet there is an inlet for the tangential introduction of the above-described diluted product flow into the pipe. The lower end of the tube is connected to a valve

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BATH ORIGINAL

Removal of liquid residue is closed. Near the lower right end there is an inlet for introduction. Controlled rate water vapor '^ The pipe is well insulated and the pressure in the system is "" on the; desired value held. The diluted product stream is preheated to 50 ° C. and continuously introduced into this first distillation column, while the column is kept at 50 mm Hg pressure and 1360 weight r 10: ir · V / ccs ^ vapor with one atmosphere is introduced into the column. vapors are continuously above the radiator withdrawn liquid (2370 parts by weight), the 16.2 wt -. ° /> water and less than 0, contains -1 fo Isöbuttersäure is continuously drawn off the bottom of the column and fed into a second concentrating means.

• The second stage is structured as follows!

An inner glass tube with a length of 25 cm and a diameter of 2.5 cm with an outer glass jacket of 3.5 cm is connected at the upper end to an overflow container made of glass, from which the dilute reactor stream contipul borrowed as a thin film over the wall of the Inner tube, which serves the rv ■ distillation chamber, runs out. The top of the column is connected to a cooler, which in turn is connected to a vacuum pump. The lower end of the tube is closed by a valve through which the residue can be drawn off. In the 'space between ae. Äthylenglycoldämpf.e are condensed in the inner and outer tubes in order to supply heat through the wall of the inner tube for evaporation. The temperature is controlled by changing the pressure in the ethylene glycol system. Vapors are continuously withdrawn from the column into the cooler, and the residue that accumulates at the lower end of the Scü-V "is continuously withdrawn. From the lower Encuj

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A stream of nitrogen slowly flows through the kojor, r. guided. The pressure in the column is operated at 25 mm Hg> - hall.en, and the maximum value that the temperature cn Errei; ,, 160 ^w C. The residence is in the column is · "■ 5 seconds. The remaining liquid (2140 parts by weight) is continuously withdrawn from the bottom of the column and parts of it are returned to the reactor as a circulating catalyst mixture, while the remainder is branched off

Example 3

The procedure of Example 2 is used in alien. essential Repeated details except that only the second stage of the distillation system is used. The feed to the distillation system contains 12.3 % By weight isobutyric acid, 9 »1% by weight water, 49.8% by weight H 1 SO, and 28.8 wt% olefin sulfonation products. the Wall temperature of the column is 160 "C. The residence time;" of the liquid in the column is 5 seconds the Dr *: 22 mm Hg and the nitrogen flow rate 30 corr. per minute (normal conditions). The distillation residue, rrri (. contains 0.8% isobutyric acid and 1.5% water.

This example shows that a one-step destination procedure can be used to separate carboxylic acid and water from the reaction mixture.

Example 4

The procedure of B & ispiel 2 is repeated in all essential details with the exception that only the first stage of the distillation system is used. The feed to the column contains 14 »8 wt .- /. Isobutyric acid, 9.0 wt.% Water, 53.8 wt.% H2 SO.

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; - ■■> ; - ig -

and 22.4 wt % olefin sulfonation products. The Boachickungstemperatur is 5O ^U C. The supply of V / aaneidompf with an atmosphere in the column is in einesr amount of 42.0 parts by weight per 100 part by weight of "feed. Major pressure in the Kolonn · - is 5O.mni Hg The distillation residue contains "0.6 fo Isobuttersilure, 15.5% Wasaer, 59% H 3 _f SO _y and 24.6 # Olefinsulfonierur;. ₀ '-

- ^c 4
Products. '

This Beispiel.zeigt also that _a ter durchgeführi from the Reaktionsrnischung a single stage distillation for the separation of carboxylic acid and W; can be.

d 0-9.8 37/22 2 4

'■ ": ■ ^; %"'< ^{Cl r} " ^: "'' ■ ¹ ^ ^ '' BAD ORIGINAL

Claims (2)

Process for the production and isolation of a lower aliphatic acid * durefc diasposition of 00 with a lower aliphatic olefin with 5th rock 8 Eobleastoxi. * Camouflage in the presence of a Sch * refelsäjaar0ntiiailtendsn catalyst and addition of water to the so aged product iadureh marked out that one ali-seeds and knives from the verdösustea Fp-Giäukt-Btischuag with a B ₁ -UCk of less than 300 ma Hg and elaer ^ eapearatur of less than 200 "C © meatilliert, bi« practical the entire aliphatlsche Säuare is distilled over and the water constitutes less than 20 f> of the Bestillationsrückstands, and the method using the D-estillationarückstaßde as sniff! repeated acid-containing catalyst *. 2. The method according to claim 1, characterized in that the distillation is carried out in the presence of steam for heat supply and for stripping ρ 009837/2224