SU583764A3 - Method of preparing saturated hydrocarbons - Google Patents

Description

one

The invention relates to methods for the production of high-grade hydrocarbons, so-called light oils, and can be used in the petrochemical and petroleum refining industries.

By production of svstlgkh oils in

On an industrial scale, one of the most widely used methods for removing unwanted compounds is the sulfonation method, for example, using oleum containing various amounts of sulfur dioxide 003 1.

However, in the form of a resinous mass, a large amount of insoluble sulfonic acids is formed, containing many soluble sulfated compounds that cannot be practically used.

In addition, sulfonation is carried out with the use of a large amount of oleum, as a result of which a significant part of monosulfonic acids soluble in oil decomposes with the formation of insoluble polysulfonic acids, which are almost impossible to use.

Also known 21 is a method for producing naphtha hydrocarbons from petroleum

2

The fractions with the initial boiling point temperature of 320 ° С by treating the raw material with x-aeral sulfur dioxide.

{Gaseous; sulfuric anhydride is obtained proportionally by burning (the calculated amount of splasic oxide sulfur, followed by oxidation of sulfur dioxide and anhydride

To reduce the reactivity of sulfuric anhydride, it is diluted with a carrier gas consisting of nitrogen, small amounts of oxygen and sulfur dioxide.

The resulting resinous mass containing HepacTBOpHNtHe sulfonic acids is separated. The product containing the solution ofHN-bie sulfonic acids is neutralized. The purified, saturated hydrocarbons are separated.

The disadvantage of this method is the low yield of the target product, the piece of un-sulphurized raw materials and sulfonic acids, soluble s oil, it is difficult to separate from the insoluble resinous mass, consisting mainly of polysulfonic acids.

In particular, when the content of sulphi 2JX sulphide is not present in raw materials relative to FAST (for example, more than 20), the image is psycho-resinous maesu, cocTOfiKyKj 3: i i FoXYLOTE. Chr ;; ЗБ: -:.; .: D) piles ::: ;; ; -: i from the target CRP. g iieb; trif girswakak sedime T; 11ip ml 1 -mImKbp with: -. 1o :: nst, so kpk e eka) -: fH rgakts: -; he iiiJX mass 11a: 1pub i-i. with g and CC and) or LseiiTp vasoE (when seg.imy fug. Except TOGO; CH9M ;;;:; KSS1. Molecular weight to the temperature of the boiling point of the processed raw material; hem vp.e TiSMurture sulphirr with neither, that - vioxreT lead to r; roG9kanii pooby x pE; a :; f; such as vinriMMepi-Sa ;; polis; ul: p acid. node1; that L1:) and leads to loss of sul1; IrovaI to:.: Soadineni-th. soluble B oil, to obraz; An abundant excess of —Enother amount of cepnOi o of anhydride, which must be removed from the waste of sh. The purpose of the invention is that of the first 1 ;; - 1e yield of the target product - it is achieved by the fact that the oil fraction with the temperature of: the boiling point above 320 ° C and the oil fraction with a boiling point of 120-180 ° C, containing dui 2 --30 dex.% Aroglastic compound ;, mixed in a BGCOEIOM ratio of 1: 1 1: 1, treated with a sulfur-like anhydride with a mixture of precipitate of resinous masses containing insoluble sulfonic acids from the product. containing paci-EOriivbie sulfonic acids, followed by neutralization of the latter; Ci: iapation fraction of purified hydrocarbons and raego Jool fraction. Characteristics of the original): Average molecular weight Density: 0.865-0: 39 Kinematic viscosity at 37, is 12–35 Contents of sulphurized compounds, wt.% Boiling point. ° C Characteristic of the added oil fraction -: Temperature boiling. With the content of sulfated compounds of weight. % 2-3 O, up to G1Ochtitelno 10-30 As a result of pre-mixing, not only the structure of the raw material is changed, the sweetness of what is, for example, a decrease in ecology, a decrease in the reaction temperature, and a change in structure resinous masses, sostayash.iH kz polysulfonic acids more than -economic molecule with sulfonangel compounds,. formed from h; i: -. :: ypb-H: jCBr.i: HH iodine cmd :, (syishi) from I yP :: G: - ts less n zhim., whiter than ecu-1I .; ii y &p};;ivaet;-( classics | e;.: O: - less processing :; and from the first product, Pisle sulphirocanic production obbatyuyag ob: ch'l:; 1 year,; on-c b neutr. :: d: l: zan: ik;;:;:.: io;: iuu npcMHiaxv: ,, tach next,. B OTsO, iSVGg ;; .- ti .aCTidO /, followed by) agon; oh send bolaoz Scic eco.olo: .ul: l en; ::: - :: -: .- ь; ; .-: d from the nmcommodule pk:; - ;;;; , t-c ;: з hkf.ia m: ..:. upper limits-; JMnePsTvTu x; - g-; g: -; mod- :: -: ullr:; oops; J.K: J. DOT; OK TTj at C OST For sulphurization, I --.-L.-use to oleum. After the distillation of foacgy, the cleansing hydrocarbons of gsgl / g fraction of 20-20 ° C and Lpakdkyu szels-on and avon), c M, .- - 1. : excess from s; t ElNogma-y-iK letters oxidase s:: 5a: s; ay; : his addition ln-chdug-d J s: - t; ch: c in l a c a l h 3 a ;; oh oh a court hand; ü; nd (in,;): 6-1 O ccpiicrc mixture of nitrogen and xx gas, 3 alparat ldg ;; u :: фир фир с rfs; - sg.; they rule at the same time .-. , 4io feedstock Foak g.: Tempegatura Ki;: yen 12028C C and Gas-like sulfuric anhydride diluted with gas-Nose: and spruce. the main ones are:.; ofjpasobi from nitrogen and small Liinx amount: I1 - :: esTE. syrnous anhydrite: go to oxygen. The apparatus for weaning sulfuric anhydride consists of a device for melting seoi. kameyuy ii-mon nor sulfur and 6si.jHH for catalytic OKHCjiSHHR-er; wc: rc; -o anhydride gg; grny, Gas, Bb: hod; 7p .; th 13th of hr: -; , contains 5-i2v; L;: -; Dpoch Thu:.: -; D - ;; o: syriy mu soder: "an-5K s-er; ogi angI1ch, ida, obtained with a smigant ;;, he rasschil /.-nky sulfur. Are similar; -; In other words, DOSING: h - ::; fused cho serur. It means:: OsBak, S and sulfuric; Ho-1g; Ig-; y: h /: Aoat. This is necessary in order to dose sulfuric anhydride in an amount corresponding to the molecular weight and average content of sulfurized compounds in the feedstock.

The sulphurization unit is equipped with a stirrer and a heat exchanger, such as a coil,

/ Hydraulic mixture, which is removed from the sulfonation apparatus, is insoluble. polysulfonic acids are neutralized, soluble monosulfonic acids are separated and distilled in a column.

Sulfuration can be carried out in several successive stages, using successively located apparatuses in which sulfuric anhydride is poured in parallel. Also included in this scheme is a separator for separating insoluble materials and a neutralizer separator for separating oil soluble sulfonic acids.

Example 1. 160 kg of feedstock (T.p.5 320 ° С, average cop, weight 320, up to 25% by weight of sulfurizing compounds) are mixed with 40 kg of kerosene fraction 140-2b ° С, containing not more than 25% by weight of sulfury F x compounds, at 35–40 ° C, 27 kg of sulfuric anhydride mixed with carrier gas (7% sulfuric anhydride) are treated,

Get 61 kg of green acidic resinous mass, which is burned. In addition, 164 kg of cool oil are obtained, which are progressed with an aqueous alcohol solution of hydrochloric acid solution. 14 kg of oil-soluble sulfonated products are recovered from the npONOiaBHoro alcohol solution.

At the same time, 151 kg of hydrocarbon mixture 5 containing no sulfonic acids are obtained, which is distilled to obtain 29 kg (97%) of purified kerosene fraction 140-260 0 as a slurry and 100 kg of purified light oil (92% by weight of paraffin hydrocarbons) as a bottom liquid .

The resulting fractions of light oil and kerosene can be further processed with 1% bleaching clay.

Example 2: 150, kg of feedstock (bp-y, average mole, ac 370, 30 weight% sulphurized compounds), mixed with 50 kg kerosene fraction 150-280 0 containing 25 u % sulfurized compounds, and absorb 27 kg of sulfuric anhydride, diluted with carrier gas (content of sulfuric anhydride 7%), at 35-45 C.

At the end of the reaction, 67 kg of a green acidic resinous mass of n 1 bO kg of acidic oil is obtained, which is shed with a solution of sodium hydroxide, and 15 kg of oil-soluble sulfonated compounds and 145 kg of purified mixture are obtained (Ke of acid holders and a mixture of kerosene and light oil products

Cr; distilled n is obtained; 37 kg of purified kefosin and 103 kg of distilled gc-gproctes are obtained. The Hirsc products are harvested for bleaching ;; riHKCf,

On a fyog; -.} -Shorogei installation scheme with a cr-ay “3 four reactors l --- i; Providing a 5-second peremegpivacch device

A jumpbutter is sent to s reactor X through line 6. Those that go out 5 with rasMf are nccapled at the top of the -iiscTK pe .--: TODOF i - 3 per second

GruiOPROVO. 7- V, СО6ДК:; Sf-: t5fc5n "с

O6iua-i 1р. 10 IasKf in-capValM}} in the Haggai ve reactor part 4,

0 17OD; og E mid-: p- reactor i through pipe-laying J, I j. close to the Ezk-to-regiae - - ;; - device 5.

Well, the GPsrap reacted with the gas boiling agent with the reagent, pos5 tug-akyui. PS of the pp 11, remove CHHsy short-circuit reactor 1, pass through the incinerator;: gp.spobobmenkk i And to the pipeline 1 VTGEUOT to the collector of the reactor 2;: pgr d also:; a: to the external device 5.

Е pjpKTOpb; 2 f I and 4 are parallel in EG: .it r 2coO ;:; i; H;,: JP reagent on tru-pcpojp-v; . h L,; n 16; who sour: sleep; Oopy G -Hi-; -; which 7 Trubopro ;; - one 1 4 f l. 5 п I р р;: polo Keny bgpeko s; perg1 - gp nzy ::: h: - r prona -; 5 Lasts s - ;: 2s; g; s-: epg19 ka -: 1-gb ;. dgspersni

KogighesG ;; about fasocopasHuro ry; y; gakta, i: O.pt-K aimigo and rrrltsyy 2: 3 to 4f znach1 gal: 0 Role: ;;;, cvolchestea, - enrolled: .c: gs1 3 E: azg; op 1 f where, with Osnoen, proliferation of a mixture of reagents

Roy.slOrg;:, 2,3 n 4 takes place significantly .; Glacapcion is insoluble: Ll coeAHKeiiiP;., formed by a series of sulfur-containing aromatic hydrocarbons. These deposits remove the 1ch u-iu period continuously through the i8fl9 discharge pipes and the 20 o. General ridge 21 o

Smayi Eir: chKh products of the HS reactor and vyzoddt PS pipeline 22f is fed B reactor 3 .. & from it via the pipe wire of 73 n reactor 4 (closer to the per 6 iekuvzi. devices 5), Nz reactor 4 o4 fUie; Upre the mixture through the pipeline 4 and 4 ЗКРГРЙ7 Ff and т и д и и д

Срл1: Firoza P1e takes place at the rate of 15% total amounts of C; alkalir of the agent. The use of the drying agent in excess allows siGn to be sulfonated; jOCTbK. excess recycle agentB v 1

FIG. Figure 2 depicts a variant of the process when a significant amount of deposits of insoluble ferric sulfosulfur compounds are already formed in reactor 1. In this Case, insoluble deposits are withdrawn from the reactor through pipeline 2, and the reaction mixture is fed to the reactor through pipe 26.

FIGS. 3 and 4 show diagrams of installations using reactors of various designs. Each reactor is divided into an upper reaction zone and a lower decantation zone or separation.

A mixture of gaseous and liquid reagents is continuously withdrawn from the top of the separation zone and is recycled continuously into the upper part of the reaction zone via a 2: 7 circulation pipeline,

Fig. 4 depicts a shrill cyoin pipeline that is divided into sections at a given point. One section 27 is designed to supply part of the liquid selected in the separation zone to the reactor and the other 26 to supply part of the liquid to the next reactor.

When continuously recycling the liquid mixture of compounds that have already partially reacted with gaseous reagent, there is a partial selection of reaction products in the form of insoluble compounds through pipelines 18, 19, 20 and 25,.

Fig, 5 shows the reactor 2 () The upper zone of the reactor is equipped with jackets 23 and 29, and the bottom of the DZ and 31, Funnel. section 32 ends with cylindrical conduit 33f creating an annular chamber 34 for receiving a LIVER mix, which is separated from the insoluble resinous mass deposited on the bottom in the separation zone.

To prevent displacement of liquid jets coming from the reaction zone with an insoluble mass and destruction of the sediment of an insoluble mass, the cylindrical pipe 33 expands its lower part and goes to the transverse baffle 35. The baffle prevents the liquid from mixing with the resinous mass.

Using a recycle pump 36, izdvigki 37 regulates the flow of insoluble, mass escaped through conduit 38.- The heat exchanger 39 works in conjunction with jackets 28-31 to maintain the temperature gradient between the separation and reaction zones. For this purpose, an annular heat exchanger 40 is provided located centrally cylindrical pipeline3

The choice of installation patterns depends on the desired degree of purity of the final product and the initial composition of the raw materials,

In addition, the number of reactors (see Figures 1-4) is not the limit; it can be more or less than four

Depending on the capacity of the plant, it’s a smaller number of reactors pasfrio to two.

Example 3. A test was conducted using feedstocks (0.76 at 15 ° C) of the following composition (wt.%}

Normal Paras 9S

Aromatic hydrocarbons 1,2

Non-paraffin hydrocarbons 2

Sulfur25rr

Normal paraffins contain (in wt.%) 1.4 С, о, 7.4 С ,,, 10.5 С, 16.8 С, g, 14.6 С „, 10.5 С, 5 р С, , 10.0 CU, B, 9 C, g, 5.2 C, 9, 2.7 0.20 2.2.

The mixture used for sulphurization contains 7% sulfuric anhydride, sulfuric anhydride to 92p81 omasi nitrogen and acid.

dbjpbe, fed to reactor 1 via pipeline 6 (Neo); the required amount of sulfuric anhydride Q is directed through pipelines 14.15 and 16 to reactors 2.3 and 4, in an amount of 0.65 Q, 0.25 Q and Odo q, respectively.

At the initial stage, the installation usually supplies 10% more sulfuric anhydride. Unreacted sulfuric anhydride from reactor 4 is recycled to reactor 1.

When sulfonating 10% of the sulphurized compound dispersed in a large mass of the non-sulphurized product, no essential formation of insoluble acids is observed.

At the end of the reaction at the initial stage, pipelines 14, 15, and 16 serve sulfuric anhydride in stoichiometry: chesky amount.

But since an aromatic compound comes from Reactor 1, already sulphurized to "10%", it turns out that there is always an excess of sulfuric anhydride in the last reactor, which provides for the sulfonation of the last traces of aromatic hydrocarbons when sulfuric anhydride is reused via pipeline 11.

Accordingly, the content of non-sulfated aromatic compounds exiting through conduit 24 can be reduced to several parts per million (ppm),

When processing OO kg of raw material 0.85 kg of sulfuric anhydride, 2 kg of insoluble resinous mass and hydrocarbons containing 25 ppm of aromatic hydrocarbons, 5 ppm of sulfur, 98% of normal paraffins and 2% of isoparaffins and cyclans are obtained.

Example4. As a raw material & lie: a paraffin-based mixture of hydrocarbons containing {wt.%):

Saturated hydrocarbons 80.9 Aromatic hydrocarbons 18.1 Compounds, containing: Hydrogen and sulfur 1.0

From 100.0 kg of raw material, 78.0 kg of purified saturated hydrocarbons, 15.5 kg of soluble petroleum sulfonates and 20.0 kg of insoluble gummy mass are obtained.

Of the 13.75 kg of sulfuric anhydride used, 2.7 kg is consumed to obtain soluble petroleum sulfonates with an average molecular weight of 460-470.

PRI me R 5. Take a mixture of coal. hydrogens on the basis of cycloparaffins of the following composition (wt.%):

Identified hydrocarbons 82.0

Aromatic Hydrocarbons 17.5

Compounds containing

oxygen and sulfur0,5

From 100 kg of the initial product, 78.5 kg of purified saturated hydrocarbons, 18.0 kg of soluble petroleum sulfonates and 15.0 kg of insoluble resinous mass are obtained.

Out of 11.62 kg of sulfuric anhydride, 3.15 kg is spent on obtaining dissolut1 "from the neftyan sulfonate

The advantages of the proposed method include decreasing the yield of the target product, improving the separation of polysulfonic acid resinous masses from the purified product, lowering the sulfonation temperature, which allows preventing or minimizing side reactions, such as the formation of sulfuric anhydride.

Improving the quality of sulfonic compounds soluble in oil.

Claims (2)

Invention Formula 1 A method of obtaining saturated hydrocarbons from a naphtha fraction with an initial boiling point above 320 s by treating gas with sulfur. anhydrite with the separation of sily leafy mass containing insoluble sulfonic acids from the product containing soluble sulfonic acids, followed by neutralization of the latter and separation of the purified saturated carbohydrates, which, in order to reduce the target product output, inconsistent raw material mixes the waste. otkoshenny 1: 1-7: 1 with an oil fraction with a boiling point of 120-280 Cj containing aromatic compounds in the amount of 2.0-30.0 the resulting fraction of valuable hydrocarbons purified by us p bring to a run Sources of information taken "90 attention in the examination: 1, Yu.N. Shakhtar, et al., Oil-soluble sulfonates. Gostoptekhizdat, 1963, p. 15, 2.Patent NDP 51405, Cl. 23 in 1 / Q5 1966. . 21 (Rsh.2. sixteen h gii 1LZ