JPS5899427A - Treatment of sulfuric acid flow to give improved thermal stability - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates generally to the purification of spent sulfuric acid streams produced in the production of alcohols by the contact-hydration of olefins.

Every year, a large amount of alcohol is produced by the catalytic hydration process of olefins. is then mixed with the ester-containing liquid to hydrolyze the ester to produce the desired alcohol, and the desired alcohol is generally heated with steam or other heating fluid. Collect by stribi/da. Thus, a dilute sulfuric acid stream is produced which, for economic reasons, must be recycled to the absorption stage after being treated to concentrate the sulfuric acid volume.

Organic impurities in these various sulfuric acid streams accumulate due to this continuous acid circulation, and this accumulation deposits carbonaceous material on the interior surfaces of the process equipment.

These carbonaceous deposits, which result from the thermal decomposition of organic impurities (1 coking), can foul the equipment and significantly reduce the flow of liquid through the equipment. The physical removal of these deposits, such as by periodically necessitating and facility interruptions and manual scraping of soiled surfaces, requires considerable human labor and service interruptions. It is costly and results in a significant loss of annual capacity.Moreover, the carbonaceous deposits thus removed are a waste of waste materials, and these
The need for safe deposit of goods creates additional costs and attendant environmental problems.

Various methods have been proposed for purifying various used sulfuric acid streams.

Certain methods of regenerating used sulfuric acid by air oxidation of organic impurities are described in US Patent No. 075°=34A.

U.S. Patent No. 3. /DaS, No. 010, in the presence of activated carbon dilute *l! A method is described for removing metal impurities from dilute sulfuric acid by reacting it with excess hydrogen sulfide and then decomposing the excess hydrogen sulfide with hydrogen peroxide, also in the presence of activated carbon.

Alkylated refinery sludge containing undesirable organics produced during petroleum refining is described in U.S. Patent No. 3, tI77,
No. 1144, in which alkylated azaleas are heated to dehydrate and desulfate the sludge, followed by a complex series of processes to produce pure sulfuric acid. and earn 1 profit.

The spent (III stream) produced in the nitration of aromatic dehydrogenates such as toluene is disclosed in US Patent No. 3, fj
&, No. A73, nitrocresol and other phenolic compounds are further nitrated organic compound impurities to be completely oxidized. Such oxidation is necessary to prevent the formation of trinitro-substituted aromatics, which are highly unstable and can be violently explosive.

U.S. Pat. and organic impurities tCo
It is stated that it can be completely oxidized to T gas and water.

U.S. Patent No. DA, /! No. 3, No. 3, pertains to a method for purifying a sulfuric acid stream containing organic impurities by the use of a Haruka acid steam jet and multiple steam Asahigaki stages. In this method, an oxidizing agent such as nitric acid, hydrogen peroxide, or carboxylic acid is added in one of several stages.

The impurity content of spent sulfuric acid streams produced in various processes and their critical process characteristics vary widely.

Thus, the above-described processes are inadequate in their use of K in the treatment of spent sulfuric acid streams produced in processes such as in the hydration of olefins for alcohol production.

According to the present invention, a spent sulfuric acid stream produced in the hydration of olefins in alcohol production and containing organic sulfonic acid impurities is treated with ozone, peroxide, chlorate,
peroxydisulfate, and mixtures thereof, in an amount less than a stoichiometric equivalent of the sulfonic acid impurity. Partially oxidized from sulfonic acid impurities to form large organic compounds and thereby increased thermal stability, i.e. even if the sulfonic acid impurity is produced, untreated used IIM at a good temperature 31 is produced at a lower rate than that produced in the stream, and is processed to produce 9-sulfur flyl, which is then processed to remove harmful organic impurities.

The inventors have discovered that i of olefins for alcohol production.
The fouling problem associated with the formation of carbonaceous deposits in the i* contact hydration process is reversed by the chemical reactivity that is produced as a product in the catalytic hydration process and easily decomposes into coke and tar at high temperatures. Organic sulfonic acid impurities in used IIM
We have surprisingly discovered that these fouling problems can be eliminated or greatly reduced by the method of the present invention, which partially oxidizes the organic sulfone impurities present in the stream. did. Also, book i
The method of Ming provides a treated sulfuric acid stream containing greatly improved thermal stability and the treated sulfuric acid Rt, after concentration,
We have unexpectedly discovered that it is possible to greatly reduce the amount of carbonaceous deposits produced by thermal decomposition of organic impurities in the olefin water supply process while recycling it to the olefin water utilization process.

Treatment of spent sulfuric acid streams obtained in olefin irrigation (by the method of the present invention) eliminates or substantially minimizes equipment fouling problems associated with the build-up of carbonaceous deposits on process equipment interior surfaces. Turtle.

The method of the invention will now be described with reference to the accompanying drawings. In the drawings, like numbers refer to the same or similar elements. Referring to Figure 1, an olefin, e.g. /molecule a
Aliphatic olefins having primary carbon atoms, preferably 2 to 4 carbon atoms, such as ethylene, propylene,
Butene, (ten, octene) in 2! From absorption tower 1
In the absorber column 1, the sulfuric acid is brought into contact with a stream of concentrated sulfuric acid introduced from line 8 and the sulfuric acid Klk is recovered (at least in part) to form the corresponding sulfuric acid alkyl ester.

The olefin to be sulfated can be obtained from any available olefin source, such as cracking distillation of carbonaceous materials, but
41, cracking of petroleum hydrocarbons as carried out in petroleum refining of mineral oils is also obtained. The olefins used in the present invention are usually also obtained by careful fractional distillation of cracked petroleum gases and are preferably highly unsaturated hydrocarbons, especially diolefins such as tutadiene and the like. Yes.

Examples of olefins that can be used are ethylene, propylene,
Lower branched and straight chain alkenes, such as butenes (
i.e., alkenes of 2 to 6 carbon atoms).

Selected Olefin Feed - The sulfuric acid R6 used in the oxidation process is at a high flow rate, the exact sulfuric acid concentration depending on the olefin used, reaction temperature and other conditions. However, in general, the sulfuric acid flow @ is about q! for the sulfation of ethylene or propylene! -9
9 weight, good i make about 6! -9 weight - of sulfuric acid, preferably about I for reaction with butene or higher olefin feed;
It contains sulfuric acid of S- to θ weight-.

The temperature and pressure used within absorption tower 10 also vary depending on the olefin, acid concentration, and other factors. Generally, a temperature of about 0.degree. C./0.degree. C. is used, and the pressure is sufficient to maintain the desired liquid phase within the absorption column. In terms of equipment,
Propylene is produced at a temperature of about 90°C to 10°C and a pressure of about 03°C to 100°C (100°C to 00°C).
absorbed at a pressure of pslg).

As shown, the olefin and the sulfuric acid stream are contacted in a countercurrent manner, and the sulfuric acid stream is introduced into the top of the absorption column.

The unabsorbed and good gas is passed from the upper part of the absorption tower 10 to the conduit 7.
If desired, it can be recycled into the pipeline or subjected to conventional MIIK treatment, such as treatment with caustic S*. The production 'IIIR, usually referred to as 1 extraction 1[I, is 2 in 4
a stone containing an alkyl ester, such as diethyl sulfate if the olefin is ethylene, or di(impropyl) sulfate in the case of propylene 1III conversion.

The concentration of alkyl ester in extract stream 4 is not critical and can vary within a wide range. That is, the extract is generally
One yield of lower alkene (eg propylene, butylene) contains ~30 weight portions of edible alkyl esters (4-noalkyl esters and dialkyl esters).

In stage 1K* of the water conservation process, the alkyl ester is hydrolyzed and the corresponding alcohol, e.g. Add water through line 1. The method of contacting the water with the extraction aII is not critical;
Various methods, including adding water to the extract (method shown in the figure) and - contacting the extract with water with stirring in a separate reactor (not shown in ml) This method is used.

The amount of water added to the extract is also critical and has a wide range of 1
! IK can change. Generally, about 0.3 to 10 parts by weight of water is added to the extract per part by weight of alkyl ester in the extract. The important thing is not to add too much water. The addition of water to the excess water only increases the dilution of the extract by 49%, which will be discussed in detail later, because the excess water in the kernels must be removed in the primary and detailed steps. be.

The dilute extract thus obtained is distilled, generally containing about 30-40% by weight of sulfuric acid, more preferably about 30-40% by weight, and then distilled over 4 passes per line. (
(herein referred to as 'alcohol-forming group I), and the produced alcohol is recovered from line 18 as an overhead product. The overhead alcohol product is then transferred to one place lI!
The alcohol is then sent to a conventional processing step 1 to produce alcohol of high purity.

The 4-product is an alcohol-forming group through twin 241!
The sulfuric acid is discharged from the sulfuric acid stream and generally contains about 140 parts by weight of sulfuric acid, preferably about 45 to 50 parts by weight of sulfuric acid.

In the usual method, alcohol production is carried out by
The distillation column is directly sent to another seven distillation columns (hereinafter referred to as ``1 column'') and the water is distilled in the column to remove water as a top product. A second bottom product is produced. These thick bottom products are generally cooled and recycled to the final K11IIL step.
Sent to storage IE.

According to the embodiment of the present invention shown in Section 1IIK, about 30 to
40% by weight of HISO4, organic sulfo/lII impurities, and t-containing alcohol producing tower 11 from the aqueous housing is sent through line 24 to the reaction zone eO, where it reacts! -/... is brought into contact with a controlled amount of oxidant introduced into zone 60 from 纺饋廖BISHUNtILt-, RY@2. The organic sulfonic acid impurities are generally at least about 700 ppm by weight, typically at least about 900 ppm by weight. θOO〜so, ooo
ppm by weight, most typically about /ko, θ00-koo,o
oo weight ppm amount, alcohol production 44 hawk product 2
Exist in 4.

These alcohol producing tower products to be passed through the process of the present invention can contain 4,000 ppm or more of organic sulfo acid impurities.

The organic sulfone impurity generally has 1 to 6 carbon atoms in the organic moiety, typically 1 to 5 carbon atoms and at least 7 molecules in the organic moiety. It typically contains 7 to -5 sulfonic acid moieties (-5OIH). When represented by the formula R80sH, %R# represents alkyl, aryl, alkenyl, alkynyl, alquaryl, aralkyl, cycloalkyl, polynuclear aryl, heterocyclic group, and 7 or more members of these groups. The hydroxy group tX can be selected from the group consisting of a keto group or a carxyl group or a sulfate group or a derivative group substituted with a mercapto group or a sulfono group.

When %R1 is alkyl, the arul group can be branched or straight chain and generally contain 7 to 71 carbon atoms, usually 7 to 6 carbon atoms. . Examples of such alkyl groups are methyl, ethyl, isopropyl, pentyl, octyl, dodecyl. When R1 is cycloalkyl, the cycloalkyl group generally contains 3 to/co carbon atoms, usually It can contain 11 carbon atoms. Examples of such groups are cyclopropyl, cyclonotyl, cyclohemonyl, cyclooctyl, cyclododecyl. An example when 'R' is an aryl group is phenyl. When 'R1 is a polynuclear aryl, the 1RI group is such a polynuclear aryl, which generally has aromatic properties, is naphthynyl, anthrathyl, 7-enanthrenyl. 1
When RI is alkenyl, the alkenyl generally contains 31 atoms, typically ri-~6 carbon atoms.

Examples of such alkenyl groups are ethynyl, butenyl, hexyl, decenyl. When %R# is alkynyl, the alkynyl group generally has 2 to 72 carbon atoms, usually 2 to 6 carbon atoms. contains. Examples of such alkenyl groups are ethynyl, butynyl, propynyl. ′
When R# is alkaryl, the aryl component generally consists of phenyl t+ tolyl and the alkyl component is
Generally contains 7 to 72 carbon atoms, usually 7 to 6 carbon atoms. Examples of such alkaryl groups are tolyl, m-ethylphenyl, 0-ethyltolyl, m-hexyltolyl. When %pl is aralkyl, the aralkyl group has phenyl or alkyl-substituted 7-enyl as the ring component and 7 to 72 carbon atoms,
It usually consists of an alkyl component having 7 to 6 carbon atoms. Examples of such aralkyl groups are benzyl, 0-ethylbenzyl, and -butylbenzyl. %B
When 1 is a heteroiso group, the group consists of a generally known compound having at least seven 6-/co members st. Examples of such complex complex groups are furyl, pyranyl, pyridine, biridyl, dioquinyl, tetrahydrofuryl, pyrazinyl, /l oxazi.

Typical examples of such impurities are -~da wI & bulky alkenyl sulfonic acids, -~da hydroxy-substituted alkyl sulfones with ~da carbon atoms! and mixtures thereof. An example of a human tetraxyalkyl sulfone is C
HmCH(OH)CH(CHs)SOsH.

HOCHmCHt CHtSOs H,CH@CH(O
H) 5O4H.

CHm CH=CH8OiH'I! What is it? The most elementary organic fractions are the carbon atoms in the olefin feed introduced into the absorption column 1, depending on the number of carbon atoms in each organic fraction.

The oxidizing agent is at least 47 members selected from the group consisting of ozone, hydrogen peroxide, chlorate, chlorine salts. Examples of such salts are N)-14''% alkali metal, alkaline earth metal chlorate and peroxydisulfate compounds.Thus, examples of oxidizing agents, 01HIO1 % sodium chlorate, potassium chlorate, magnesium chlorate, peroxyacid HIS104, (ruoxy diamium/monium, etc.).

Selected oxidized steel wire, per amount of sulfonic acid impurities/
Less than the full oxidation stoichiometric amount, preferably/less than the full oxidation stoichiometric amount of IO-, more preferably!
It is used in an amount less than 0, most preferably less than 1/2. In this specification, the term 1 completely oxidized stoichiometric amount l refers to the amount required to completely oxidize the organic nulphonic acid in m* to produce carbon dioxide gas (CO++3 and water). This means the commercial quantity of the selected oxidizing agent.

Since the stoichiometric amount required for complete oxidation of the organic sulfonic acid impurity will vary depending on the oxidizing agent chosen, the exact sulfonic acid present, and other factors, the amount of organic sulfonic acid impurities introduced into the reaction zone O by the present invention The amount of oxidizing agent applied also differs. The complete oxidation of elementary alkenyl sulfonic acids to dioxide longitudinal lines and water by various oxidizing agents is shown in equations α) to (V) below.

CH, CH-CHCH! So, H+/Yu H10, → Da C
O*+/j°H, O+H, 504(I)CH, CH=C
HCH, SO Karasu H+/ko01→Da Cot +JH*O+
HmSObanju/ko01 (II)CHsCH=
CHCHtSOaH+/koHtStOs+9HmO→I
I COt+Jj Hl 504 [[I
CHsCH=CHCH*SO Hatake)-1+/ko*6*O
*+DeH meeting 0 → DaCOt+KO5, 50.
Top CHI CH-CHCH! 5OIH+/Koni αO Crow→
4(COt+,?H*O+/JK(lJO1+H,sO
4 (V) The contact line between the oxidizer and the used sulfuric acid stream in the sea/60 can be carried out in a batch mode or in a continuous mode or in a semi-continuous mode. The method of contacting is not critical, thus, for example, adding a selected nineting agent to a conduit containing a spent sulfuric acid stream. In this case,
Zone O can be viewed as a tubular reactor. Alternatively, Zone O can contain the oxidizer and the spent 1III! and a reaction Al tube into which is introduced. Preferably, an oxidizing agent is continuously introduced into the spent GI stream to continuously partially oxidize organic impurities in the sulfuric acid and thus associated material deposits on the Zororyus equipment. Make sure that the dirt gap is substantially reduced.

, is essential for reactions between other agents and non-volatile organic impurities!
A wide range of Ilf and pressure conditions! ! IK changes, but
Generally about 0~770℃, preferably about /θθ~7
A temperature of 30°C is used, most preferably between about /10 and 730°C. It is possible to use 111% outside these ranges. Sufficient pressure can be applied to keep the sulfuric acid stream being treated in a liquid state, thus atmospheric, subatmospheric, and superatmospheric pressures are common. K is about -70 because of Dependency or Latin absorption! r4I~yu10deh/al
The pressure of l'-dipressure (-/S~J Opsig) is completely appropriate.

The residence time of spent sulfuric acid in the sea/11G is not critical and is generally about 10 seconds to 10 hours, more preferably about 10 seconds to 11 hours, for most effective use of the added oxidant. I am H.

It has been surprisingly discovered that by the method described above, certain sulfonic acid impurities are converted into oxidation product quaternaries which are significantly more thermally stable than the organic sulfonic acid impurities themselves. Thus, these oxidation products contained 9 used 11 m1! R indicates a permanent reduction in the propensity to build up coal snow deposits in the process equipment associated with the production and recovery of alcohol and the concentration and rewriting of the Kll 11.

Of course, the exact oxidation products will vary depending on the amount of organic sulfonic acid impurities, the amount of oxidizing agent, and other factors. but,
In general, 1 these oxidation products are composed of lower aliphatic carbs/acids (e.g. acetic acid, pro-ethanol, Contains a mixture of oxidized longitudinal fibers and carbonized carbon.

At least a portion of these oxidation products are significantly more volatile than the organo-nulfonic acid impurities. Thus, the treated nine spent sulfuric acid containing oxidation products,
At least a portion (and preferably at least a majority) of these more volatile oxidation products may be removed by further removal, such as by flushing the bottle under vacuum. It has been surprisingly discovered that in order to obtain a more thermally stable sulfonic acid, it is not necessary to remove oxidation products that are less volatile than the organic sulfonic acid impurities.

11E/llf) limmlll, the alcohol production column product treated at 1111 passes through line I4 and is sent to the reaction zone -O or exhaust #SII to the concentration im*so, and is sent to the am*so in the am column 30. The partially stratified and endangered spent sulfuric acid is then contacted with a heating fluid such as steam introduced from line 34, water is removed from line a2 as a droplet semi-product and a sac thickness of 1 isi* is produced. Takatsuki Shunryu is line 3
It is discharged from Lu. The temperature and pressure conditions within the concentrated SO are not critical and vary widely depending on the tin salt alcohol flow.

Thus, for the hydration of butene or pelopene, approximately tO ~
/ 0°C, preferably a temperature of about 10-130°C, and about -7O! 4t! 3--γθ3 noodles/-l”-ji pressure (-/
Pressures of S ~ 10 θps Ig) are commonly used.

The aqueous overhead vapor discharged from line 32 is transferred to narrow column 30.
It also contains at least a portion of the oxidation product that is sent to the column 30 and vaporized under temperature and pressure conditions.

The sulfuric acid stream discharged from line 3 is then cooled in a heat exchanger - O and then transferred to the ninth volume of intermediate storage in the third column.

This thickness ii* is finally recycled to the absorption tower 10 through the line @, and replenishment ii* is added from the line S according to the time.

If desired, a portion or all of the effluent from reaction zone IO is routed through conduit sI to a separate distillation zone 4, in which volatile organic groups and lower boiling points than water are produced by partial oxidation in zone 60. Impurities! It is heated by removing it from conduit 42 as the top product. The liquid thus obtained, which is less volatile in organic impurities than water, is then sent to conduit 4 for introduction into concentrated IIajIFsO. In this embodiment, the aqueous overhead product s2 of the concentrator 30 contains a reduced weight of organic impurities.

If desired, a portion of the bottom product recovered from alcohol regeneration 420 via conduit 24 may be routed directly as feed to concentrator 30 via conduit 211. Dew.

Therefore, in this embodiment, #l sent as a feed to the contacting zone O is a slit of the alcohol-loaded product that would otherwise be recycled as a direct feed to the concentrator 30. *It took 11 days to meet on site. Of course, within Zone 6! The S content of the alcohol bottoms product depends on the amount of impurities in the alcohol bottoms product, the desired purity level to be achieved in the treated stream, and other factors. , can be articulated by a valve 21.

However, generally at least about 70 volumes of the alcohol column product - preferably about 1 to 100 volumes - are subjected to the process of the present invention within the 1 zone for partial oxidation of the organic sulfone impurities therein. It is divided into layers.

Next, follow #I and IIK and fly a wing. For the third shade, concentrated sulfuric acid, e.g.
*+and at least/! ;00 pprn, usually about t, ooo to 3o, ooo ppm or more, more typically about 10.000-20.000 ppm
The bottom product from condensation column 3, containing organic sulfo/lIl impurities of The present invention is shown in contact with a selected oxidizing agent introduced from T2 into C/T. The liquid effluent passes through conduit 74 to Sea/T@
is discharged from. This oxidation zone effluent is then passed to a separate distillation seam/40 in zone 4, where one volatile organic impurity is removed as an overhead product through conduit 42, as described above. The resulting liquid, free of organic impurities more volatile than water, is then passed to conduit 3, and then cooled, if desired, in a heat exchanger SSO to nine bales.
It can be recycled to the container sse as described above.

Optionally, a portion (t or 1 l) of the liquid effluent in conduit T4
l) is rewritten to the concentration column 80 through conduit 731;
In the sSO, volatile partial oxidation products such as water produced in the zone TO are vaporized and passed along with the overhead product into conduit S.
It can be discharged through proper operation. By using such recirculation IIt through conduit TST, the need for a separate distillation zone 4 is reduced or even eliminated.

If desired, a portion of the liquid in conduit 30 can be recirculated to the process directly through conduit 3.
You can send it to I. In this case, the f#:, II stream processed in shea 770 can be viewed as a slip stream of the Hakko acid bottom product discharged from the concentrator 3.

The relative flow rates of liquid flow into zone 40 and through conduits T3 and lea are controlled by valves 75.77.35, respectively.
adjusted by.

In the following, the method of the invention is further explained by Example 1iliK. In the examples, parts are parts by weight unless otherwise specified.

In the examples, total soluble organic longitudinal cord (TSOC) 1lffl
First of all, the glass fiber attached to *Gafus Vacuum 7 TSUCO - past day @ (Re@ve＾ngsl 9 J$ AH,
Whatrnan Co., Ltd.) Using a liquid sample that had been passed through a nine-funnel vacuum to remove carbonaceous surrounding particles having grains larger than about 11 cm, Perakumin Total Organic Carton Analyze (=15811) (B.
ckmanTotal Organic Carbon
Analyzer (Model, 2/jB)
This is done using

In the example, the distillation of the sample was carried out using a thermometer and a length of 6 m (
9-inch) glass water-cooled cooling system and t-equipped
, by placing each sample into a round bottom flask. The liquid is stirred with Madanetic Star 2- and heated with an electric heating mantle.

At normal pressure Km, about a per minute! Distillation is carried out at such a distance that 1 volume of water is collected as condensate. l & warm f, 7 weight -
Concentrates at the normal pressure boiling point of sulfuric acid. The distillation was stopped when the temperature reached 171° C. After cooling, the condensate and the liquid remaining in the flask were analyzed for TSOC.

In addition, the condensation gas is analyzed using F-Darafi.

Heat soaking in the examples (h@at soaking)
The escape route places the thus escaped sample into a 2Jθ-2 round glass flask equipped with a temperature needle, a 9-inch long glass water-cooled condenser, and a magnetic stirrer. The flask is heated with an electric heating mantle, and the liquid is completely refluxed for a predetermined period of time while being stirred, and the liquid is distilled, and then the TSOC of this liquid is analyzed.

EXAMPLE/In Experiments 7--, the delcese which hydrates n-butene to form the corresponding alcoholic acid is also discharged and used sulfuric acid (7 Sample number 209 of HlSO4), each containing a temperature needle, a water-cooled condenser open to the atmosphere, a magnetic stirrer, and a volume of 30A peroxide water, was pressure equalized. -equ
al Ized) Addition - separate 3 with doo and t
001Pour into a three-neck round hawk flask. In experiment 1, the spent acid is diluted with water to give an exchange of 60 wt-HlSO4. Heat the liquid in each 7 Cusco with an electric heating mantle/
The temperature of the liquid 3c is [K], and peroxide water 31 is added to the liquid in order to control the exothermic reaction that occurs and to maintain the liquid temperature at ±3°C.
Add dropwise. After the addition of the peroxide volume is completed in about ls minutes, the resulting reaction mixture is cooled to ambient temperature and weighed. Before the addition of hydrogen peroxide, the acid sample was heated to 9, TSOC.
and organic sulfonic acid impurities.

Thereafter, the experimental casings are distilled to remove acid using the method described above. This re-concentrated 9 liters (12 t-1) was then taken out from one reaction flask and placed in another flask, and in the same flask was subjected to the above heat soaking at a temperature of 12 t°C. te, 1
: The amount of carbonaceous surrounding body produced by the thermal decomposition of Ill airborne TSOC which has undergone 1 degree of I-xization, that is, heat J611.
ie set.

In experiment 1, the liquid after addition of H,O is diluted with enough water to reduce the must to 60 wt. 7 - Re-concentrates the weight rice cake H, $ O, K, thereby giving a thermal history comparable to the Shun sample of the refreshing example. Afterwards, it is re-concentrated with the same heat treatment as described in the experiment/description.

In order to demonstrate the modification obtained by the method of Takaaki Moto in the reduction of the amount of carbonaceous surroundings produced in the acid, the total submersible organic carbon of the indicated am Impure HmSOa (71wt*HmSOa), which contains organic sulfonic acid and organic sulfonic acid and has been destroyed by the method disclosed in the present invention, is diluted with water to obtain 60wt HmSOa. *K Shi, next KJi worked hard, and reconcentrated it to 7-weight 11, and experimented with it/-A heat shoe comparable to Ko! A separate series of experiments is carried out, giving 9 samples, which are reconcentrated and then subjected to the above heat soak for 7 t'cK for an hour.

The hazard data obtained from these experiments are shown in Table 1 below.

As can be seen from the data presented in Table 7, the experimental hydrogen peroxide partial oxidation treatments produce sulfonic acids with greatly enhanced thermal stability. Hoot in Experiments/and- Only a fraction of the weight of TSOC in sulfuric acid subjected to 46 cycles pyrolyzes to insoluble vertically oriented solids in the subsequent thermal noking treatment.

In contrast, experiments 3 to 9 that were not treated according to the present invention
Approximately 7 g of TSOC present in the spent sulfuric acid stream
6-weight tungsten is thermally decomposed into a non-camellia pedunculated solid by thermal noking treatment. Moreover, the experiment/and the coking barrier f(
That is, in the heat soak test, the number of vertical prime solids produced in solution of /,oool) was also lower than in control experiments 3-S, which contained a much larger initial TSOC level.
6. The coking rate of the heat soaking mill is much lower than that of the rapid flow, and has a lower T$OC level.6.
7 heat treatment l1w1. It is still much lower than the coking rate.

Therefore, at vigorous TSOC levels, patch formula 1 or semi-continuous formula ta can be used in continuous format. Improve your olefin irrigation process with less concomitant coking and therefore less carbonaceous deposits fouling the wastewater treatment equipment than is acceptable! make it possible to stand up.

As a result, the method of the present invention is effective in reducing the amount of dirty acids.
cid) ' For example, in the effluent from the reaction zone about 0, ooo'nrnt, preferably about ! 00
~15000pi) m s more good news/, 00
It is possible to carry out olefin water utilization processes without significant carbonaceous fouling problems using acids with a content of 0~/θ, 0θOppm (calculated as original coal purple). Thus, the present invention was considered essential in the prior art. Preventing dirt problems,
! By removing the soluble organic fibers at all levels, the amount of used sulfuric acid used to produce 1 white sulfuric acid is eliminated.

Advantageously, the stream treated by the method of the present invention is
For example, when exposed to 750~/lO'c>K, carbonaceous solids are formed in the immature II stream under such conditions.
χ is also at least about son, more preferably at least about ? 01s Generate a vertical aptitude garden body at a small speed.

It will be obvious that various changes and modifications may be made without departing from the invention, and therefore everything contained in the above description should be construed as examples only and the qI4t-limitations herein. For example, there are seven alternative embodiments of the embodiment shown in FIG. 1, as well as one preferred embodiment of the invention! ! As a member of li,
At least about so.

The filtrate containing ppm of organic sulfonic acid impurities is discharged from the concentration column 3 at the bottom of the acid supply conduit 24, and is then discharged from the condensation tower 3, as described above. , the contact zone T for treatment with selected enemy and other agents.

to produce partially oxidized organic compounds from organic sulfoy* impurities. Thus, it is felt 't'
t,*ritt can then be sent from zone 10 back to eel reduction tower 3o through conduit T3t-, as described above.

In yet another most preferred embodiment of the present invention, selected additives are added to the I#III column, e.g.
It can be added directly to one or more points in the precious column in the solid line embodiment of FIG. In this case, 2. The desired partial oxidation of the organic sulfone impurities occurs in situ in the Shunno tower, and then 1. The more volatile oxidation by-products are transferred to the acid as overhead products. It is removed from the concentrate column and concentrated sulfuric acid is produced and discharged as a bottom product.

[Brief explanation of drawings]

1 Ila is a schematic diagram showing one condensed line embodiment of the method of the invention; pl Ia is a schematic diagram showing another solid line embodiment of the method of the invention. The drawing numbers are as follows: 4...Extract liquid stream, -...Sulfuric acid stream, 10...Absorption tower, 2...Sweeping tower, alcohol producing group, 24...Alcohol producing base bottom generation material, line, go/lnl, 40...separate distillation zone, 10...container, ・O...reaction zone, 1G...contact zone, @O...heat exchange S.

Claims (1)

[Claims] / A method for improving the thermal stability of a spent sulfuric acid stream produced in the catalytic irrigation of olefins for the production of alcohol and containing organic sulfonic acid impurities, the method comprising: , an oxidizing agent selected from the group consisting of ozone, hydrogen peroxide, a chlorate source, peroxydisulfate, and mixtures thereof; When contacted in an amount less than the stoichiometric equivalent of complete oxidation, the sulfonic acid impurity is partially oxidized into an organic compound 1**, thereby converting the sulfonic acid impurity into a partially oxidized organic compound 1**, which has good thermal stability.
*An improved method of giving mt. 2. The improved process of claim 1, wherein the organic sulfonic acid is present in the spent AM stream in an amount of at least about 500 ppm by weight. Claim 1: A tin-layered spent sulfuric acid stream containing partially oxidized organic compounds is treated at elevated temperatures to vaporize and remove at least a portion of the partially oxidized organic compounds. Improvement method described. Disease The spent sulfuric acid stream contains approximately 443-99% by weight of H,SO
8. The improved method according to claim 7, comprising: & (a) Swirling the olefin into a collection zone and collecting the olefin in an aqueous exchanged sulfuric acid 1111 [KI to produce a sulfuric acid alkyl ester corresponding to wrinkled olefin/; and (b) WR sulfuric acid alkyl ester. (C) extracting the resulting dilute liquid with axillary alcohol as a gaseous product; an alcohol production process comprising: tracing back to the ninth alcohol production zone, thereby producing a spent sulfuric acid stream containing about 4 to-ss heavy sulfuric acid and at least about 300 ppm by weight of organic sulfone impurities; (a) a method for improving a method of improving the method, comprising (a) contacting at least a portion of the used armpit acid with the oxidizing agent described in Section 1 in the cal contact zone; (e) a 1 m portion; The recovered and recovered stream from the acid axillary contact zone containing acid oxidizer compounds is combined with a portion of the spent sulfuric acid stream that has not been processed in the contact zone to form a condensation column. and removal of the aqueous vapor in an acid concentrator to produce a 1IWR stream with good thermal stability and increased thickness due to the absorption of water into the absorption sea/f: %. (a) A step of absorbing olefins into an aqueous thick sulfuric acid solution in the lk collection zone to produce a sulfuric acid alkyl ester corresponding to the mosquito olefin; (+) recovering a liquid stream from the absorption zone containing a′ and contacting the recovered liquid with water to liberate the corresponding alcohol; At the ninth stage, it is collected as alcohol and sent to the alcohol production zone.
A process of regenerating the used sulfur s+sit by modifying it, and (d) the used @lI! The stream is sent to a condensation tower, and in the acid condensation tower, the spent sulfuric acid is distilled to remove 1 aqueous vapor twi, resulting in a ratio of about 4<,5--99 weight-s2. An improved method of producing alcohol, including a process of producing a thick used ii* containing
, after d, the following work II e i The pull is f and the next is gl
(-) discharging from said acid concentrating column an occasional flow containing at least about 500 parts by weight of organic sulfonic acid impurities;
5 which was brought into contact with the oxidizing agent described in Section 5 and thus treated.
recirculating at least a portion of the 11-acid stream to the concentrator from the alcohol production zone, at least about 300 g
A spent sulfuric acid stream containing ppm by weight of organic sulfonic acid impurities is deposited in a column in a compressor.
! 1. Introducing an oxidizing sub-tube as described in paragraph 1, or sending at least a portion of the concentrated spent IUI stream containing at least about 300 ppm by weight of organic sulfone impurities to the tII catalytic zone and within the catalytic zone; Patent claims IP! one of the steps of contacting with an oxidizing agent as described in paragraph 1, and at least a portion of the sulfuric acid stream thus treated is distilled of said partially oxidized organic compound which is more volatile than water or is primarily co-distilled with water. treating at temperature and pressure conditions such that at least a portion is vaporized and removed, thereby producing a stream with increased thermal stability suitable for recirculation to the absorption zone; Improved method to remove mold. 6. The method of claim 6, wherein the contact with the oxidizing agent uses a temperature of about 70 DEG C./deO<0>C. The improved method according to claims 1 to 7, wherein the organic sulfone impurity contains a hydroxyalkyl sulfonic acid, an alkenyl sulfonate/acid, or a mixture thereof. Claim 1, wherein the number of carbon atoms in the organic moiety of the organic sulfonic acid impurity is comparable to the number of carbon atoms in the olefin.
Improvement methods described in Sections - g.