CS199840B1 - Method of refining biologically processed petroleum product - Google Patents

Abstract

1534133 Refining microbiologically treated oils PETROLCHEMISCHES KOMBINAT SCHWEDT 11 Dec 1975 [20 Dec 1974] 50835/75 Heading C5E Oils, such as petroleum oil or gas oil, are microbiologically treated, e.g. with a yeast of the Candida type, and the deparaffinized oil residue is subjected, without any intervening hydrorefining to a heat treatment followed by a distillation, the heat treatment being carried out at 250-370‹ C. for 1 to 10 hours and followed by a distillation in which a heavy sump fraction (which can be in part reheated and returned to the distillation column) and a light top fraction are obtained. The heat treatment can be preceded by washing with aqueous ammonia. The heat treatment and distillation process reduces the fouling which occurs when the light top fraction is subsequently hydrorefined using a Co-Mo catalyst catalyst.

Description

(54) Process for the purification of biologically processed petroleum hydrocarbons

The invention relates to a process for the purification of biologically processed petroleum hydrocarbons, preferably kerosene, diesel oil, gas oil and petroleum products derived therefrom.

When processing oil is used hydrotreating to remove sulfur compounds and hydrogenation nenasycenýc uUovod ^h ^ s. ^P ^ s ^ Dror NaCl Wol ^ i ^ s ^ r ^ ^r ^ tubs for OPN ^{ACTIVE Duk} TU besides changing substances which come into petroleum products- specific biological process.

Besides this ^h of Zn ^{and Mo,} that ^{the PU} with ^b u I ^{RC biologically} gi ^C to ^{EHO de} pa ^r and ^FI n ^by Van ^{I are} in ^{the petroleum p} roducts ^obs and ^F en ^{y except p} ro ^d u ^k tů. ^Substance b ^s p m ^of strap ^ikroo rgan ^{isms even if} pOTrctově tive, LA ^- area (surfactants), such as pollution.

The GDR patent no. 50 520 proposes to carry out the hydrotreatment of the biologically processed Immunoisolated ^ ro ^p NYCHA hydrocarbons. ^to Mo ^p oo ^DdeI the mi-Cr ^ rganisaiů. ^{For OBV} y p ^{from klých} ditions ^hydro refining would dream ^of Il ^b of the ^h of sulfur from Gritting ^b.

When using conventional methods hydrotreating occurs after a specified period of operation ^under RI ^DRIVING formation US ^{and aminopyridine} compounds in abrasion ^Bi in con ^t if ^t n ^{e Cmctě} and ^{- by - -} к ^{the UCP} and ⁱⁿ An ^s.

For ^Saz e ⁿ ins penetrate hl ^and outside ^{the p} řítomnost ^s to ^d at ^KTU tvoMcító Arabic gum ^{to the y-resins} and ^{as well} as the above ^ le ^ paterns ^P roducts ^s, a ^{* i} c ^h uzazování ^{m k} r ^bonisací in ^refining niin z ^ i ^ no ..

According to experience, biologically processed hydrocarbon oils contain a higher proportion of such as 1999 840

199 840 of disturbing products than unprocessed hydrocarbon oils of the same origin and in the same distillation range, for which reason the biodegradable products of hydrorafinai lead to clogging of pipelines and equipment more quickly than similar ones,. biologically unprocessed products.

^p o ^p e ^dl atentového IEU with ^p S ^p o ^o o ^{p e} Re also for ^{bl y. Therefor} Meck no. 1118 9U is in ^bi about ^l o ^{g i} c ^ky unprocessed hydrocarbon oils is known, adding to the furnish hydrorafinaoi hydrocarbon oils under the conditions of hydrotreating does not change in pairs, so as to relatively high molecular weight substances, producing resins and coke preserve during hydrotreatment in solution, thereby avoiding coking and deposition of these substances.

Further, according to German Unexamined Document No. 1,252,346, it is known to treat a portion of a feedstock liquid under hydrotreatment conditions separately from the portion which is converted into steam under these conditions.

It has also been proposed to carry out a simple distillation, as is usually used for the fractionation of crude oils to produce a feedstock for hydrotreatment.

In addition, washing processes are known in which oil products are freed of unwanted mixtures by various washing liquids.

For example, in order to remove ash-forming substances, U.S. Pat.

152 067 suggests treatment with steam at a pressure of ^p racování or hot water according to US Pat. 2,789,083.

In atentovém ^p with ^p IS Pat. No. 2 7 ^{28 71} 4 m ^ and compatibility ODS-enoic acid minerálrá ^ ^ S ^^ to, resins, asphaltenes, and other similar contaminants by washing with hot water and surfactants and in U.S. Pat. No. 2,778,777 by washing with 10% sulfuric acid.

For purifying the biologically processed oil products jsou.rovněž known multi-axis work ^p u ^t ^ ^ ^py; to AD ^M BBs ^{of ex l s h} ou em (French pa ^ nt no. ^{1 38} 4 2 ^{51, p} and ^t en ^t AC Pat. No. 3,259,549, South African patent no. 63/5430), washing acidifying agents or a combination of these procedures ·

A disadvantage of known hydrotreating processes is that the use of biologically treated hydrocarbon oils lead deposits on the catalyst and on the walls of the device in a short time to clogging, so that the device must be put out of operation, so that the deposits are removed and kontatoní ka ^t ANALYSIS ^{Tor characterized} changed. Oto ^T vyřazerá from ^O PERATION ovHvňuje in ^considerable mu n ^e e tospodárnost ^of these methods.

A disadvantage of the known processes in which hydrocarbon oils, which do not change under vapor conditions under the reaction conditions, as well as the known methods of separately treating the liquid fraction, are added to the feedstock, since it is impossible to prevent deposits on the catalyst.

By simple distillation, as it is usually used to fractionate crude oils, usable results will be achieved for biologically processed petroleum products ·

A disadvantage of the processing of petroleum products by the procedures of U.S. Pat. Nos. 2,728,714, 2,778,777, 2,789,083. and 3,152,067 is that they do not remove high molecular weight products, as well as resin and coke forming products that are disruptive to hydrotreatment, to the extent that trouble-free hydrotreatment is possible.

To ^p-party cover Úsobí ^Net of the ^{bi l} og ⁱ c ro ^alkyl processed Nym ^p ro ^{p d p} will strike utoů ^used to allow ^the

199 840 achieve perfect removal of harmful impurities only by complicated technological equipment, use of auxiliaries and a large number of operating staff.

UCE ^l em VYN & Cutting is ^Le ZT ^PU with ^{b, Y} p ^{s p} ou ^{living b} iological processed ^Uhl's díkových oil, preferably kerosene, diesel engine oils, gas oil and petroleum products produced on their basis guarantee long uninterrupted period of operation of conventional hydrotreating equipment.

The object of the present invention was to prevent the formation of deposits on the catalyst and on the reactor walls of the hydrotreating plant in order to avoid blockages and disturbances in the reactor operation.

The process for the purification of biologically treated hydrocarbons, preferably kerosene, diesel oil, gas oil and other petroleum products, is solved according to the invention by heating the biologically dewaxed petroleum product for 1 to 10 hours at a temperature between ²⁵⁰ and ³⁷⁰ ° C. , ^z is extended NACE ^separated in ^l ehkou fraction ODC ^hook gaping ^{s hl} of ^y and ^{y columns, kt ER} represents 70 to 97.5% of the products and a heavy fraction, the heavy portion. fraction is reheated and returned to teach a ^{b d b} not dividing the SLP ^{l No.} ers ^{t p} ara exchange de ^fi novaným ro ^p n ^p ro ^{characterized ucts} em destilaoe again.

At that temperature, a substance forming resin and coke, grouped in larger agglomerates (after ^l ymerace not about ^to ondenzace ^{b) or} M ^F MMN ^{and Kaj-products to} the INDIRECT ter ^{é í} in nujol ^of steam. Petroleum product is heated in this manner is fed to the bottom of the distillation column which separates ee ^{p y p} hare arachidonic that де ^of exhausted via ^{a r hy} to Dror ^fi tion. Part ^F ra ^{difficult to} CE obohaceró pr ^{y y} sk Rice and organometallic compounds reheated and separate or together with fresh raw material is again fed to the distillation column.

The desired temperature and mean residence time of the petroleum product at this temperature as well as the desired degree of conversion and steam are achieved by controlling the ratio of the amount of fresh deparaffinized petroleum product to the amount of recirculated heated heavy product.

The characteristic combinations of heat treatment and distillation of the biologically processed petroleum product are given in Table 1.

Vol^band te^plo^you for^hřv^andn^and in range^{í 250} to³⁷⁰ ° C and p^clE^dn^time with^etrvání in^range1 to 10 hours is dependent on the type and amount of resins and coke and organometallic substances^OEastern^withlo^učenin,^jas well as dest^andla^Cnim rozmez^and uhl^ovodíkovéh^O p^genusUK^{here, u}rčen ^^Eh^ok ra finaci.

To avoid decomposition of used oil products, the combination of heat racován ^{p s d} and ^p es ^til ACE Rovai ^ga Tiz ^dreaming roto ^ pressure.

L ^e HKA tailcoat ^ce t ^and kt ^the combined te ^p elným and ^d es ^the la ^{instillations} p ^os the ^PEM p ^Rede back ^{racované to} determine ^the guilt ^{is p} rnkti ^c k ^yp rosta ^la te ^to the ^yt vářej ^IC IC ^h prystyřice ^{and coke} and ^has ^ OTnání де ^raw and ^{with it on a} d t n ^and t ⁿ i ^{of harder} obMh n ^{lower level of} the ^{b ss} sah ytku for ^m n ^ého en ^teacher in pairs ^(real te ^C No resin) and a lower tendency to produce coke.

Products in this way pre-treated according to the invention, can be handled without disturbing ^influences in usual. h ^yd and y ^{or fi} to ^towering h ^of mounts ^from Enichem.

^{In the} processing biologist ^and ck ^y z ^p racovaných uhlwtáft ^ ch ^{hydrocarbon oils such} Neto kových ol ^^. which nmjí substantial content of organic acid amide ^to YC ^h Vol ^{characterized} him kyseUn meats ou ^{d, J} e be the effect of the method according to the invention improved in that the raw material before the combined tepel-

199 940 subjected to aqueous ammonia washing with aqueous and de-pressure treatment.

In addition, it is particularly advantageous if the process according to the invention is carried out immediately after the biological treatment, thereby eliminating the need to sterilize the biologically processed petroleum product.

The process according to the invention is illustrated by the following examples.

Example 1

Diesel oil distillate fraction * whose quality characteristics are given in Table 1 (column 1) are subjected to microbiological dewaxing using Candia yeasts in a continuous fermentation process.

The quality characteristics of the dewaxed oil are given in Table 1 * column 2.

The paraffinized product is purified in a pilot plant according to the invention. The parameters of the combined heat and distillation treatment are the following: * inlet temperature 330 ° C mean residence time under heat treatment 8 hours removal of light fraction 90%

The quality indicators of the light fraction are given in Table 1 (column 3).

As can be seen from the table, a reduction in the resin content (determined by chromatography) and 0 * 27% in the dewaxed petroleum product to 0 * 04% in the lightweight fraction is achieved by the process according to the invention · The ash content is reduced from 9 to 4 ppm ·

When determining the content of the chromatographic resins, higher molecular weight organic acids are also included in this content. Thus, the loss of the content of the chromatographic resins by possible ammonia scrubbing is interpreted in such a way that the ammonia water of such an acid as well as other polar substances are washed out of the bio-treated petroleum fractions.

The light fraction * obtained from dewaxed petroleum product * is then subjected to hydrotreating in a pilot plant under normal conditions using a Co-Mo catalyst * to achieve continuous * trouble-free operation of the plant for 2000 hours * ·

Table 1

Oil product quality indicator raw material (petroleum product) before processing after processing according to the invention 1 · density g / ml 0.848 0.850 0,845 2.Sulfur mass content % 1.07 1.19 1.00 BPA point 3 ° c +5 -1 -16 4 * pour point * ° C -3 -12 -23 5 * HCl HCl * ppm 5 9 4

199 940 «chrome

wt ·% 0.08 0.27 0.04 7-distillation analysis · 0 5% vol (° C) 245 249 237 8. 15 99 258 260 252 9. 45 W 282 282 270 10. 55 II 291 291 27? 11. 85 H 326 325 301 12. 95 II 350 351 315

For comparison, hydropreparation of the product is carried out in the pilot plant under the same conditions, which has not previously been subjected to a combined heat removal process ·

After 600 hours of operation, the plant must be shut down due to deposits in the contact area of the plant and for reactor clogging. · Reactor and clean »catalyst is replaced and the plant is put back into operation. Reactor ·

Example 2 ⁴

Microbiologically dewaxed petroleum distillate oil fraction, characterized by the qualities listed in Table 2 (column 1), which is similarly obtained as described in Example _19, is washed with a 24% aqueous ammonia solution. Column 2 of Table 2 · Washing will only show a significant change in acidity number - decreasing from 11 _t 8 mg K0H / 100ml for dewaxed petroleum product to 2.2 mg K0H / 100ml in washed oil product · The washed dewaxed petroleum product is then purified The parameters of the combined heat-distillation treatment are the same as in Example 1.

Table 2

Quality indicators _____ Dewaxed petroleum product

product starting material washed with ammonia water after processing according to the method of the invention 1.density at 20 ° C, g / ml 0.850 0,851 0,846 2.Sulfur mass content % 1.19 1.15 1.00 3. point BPA, ° C -1 i 0 -18 4.point solidification. Noc: 2 ° C -12 -12 -24 5.H ash content, ppm 9 10 2 6.acid number mg KOH / 100 ml 11.8 2.2 3.4 7 · high resistive mass. % 0.27 0.15 0.04

б

199 940

в. distillation <

analysis, ° C

5 % vol (° C) 235 234 240 9. 15 Dec w 249 250 255 10. 45 w 280 279 280 11. 55 в 287 287 285 12. 85 ti 325 322 303 13 95 ft 345 345 314

The quality characteristics of the light fats are given in column 3 of Table 2.

As can be seen from the table, the chromatographic content of the determined resins is reduced from 0 15 15% in the starting product to 0 04 04% in the light phase and the ash content is from 10 to 2 ppm · Subsequent hydrotreating in pilot plant under normal conditions with the use of a Co-Mo catalyst, after 2000 hours it proceeds without failure and without reducing the activity of the catalyst.

The use of the proposed method for the purification of microbiologically dewaxed petroleum products guarantees these advantages as compared to existing methods

(a) the possibility of carrying out a hydrotreating operation without reducing the activity of the catalyst and without disturbances during hydrorefining, thereby allowing the hydrotreating equipment to operate for more than 2000 hours in the long term;

b) improving the quality of biologically processed petroleum products by reducing the content of »resin and coke-forming compounds as well as organometallic impurities.

Claims (4)

BACKGROUND OF THE INVENTION 1 · Process for the purification of bioclocks of hydrocarbons »preferably kerosene» diesel oils »gas oils and other petroleum products» characterized in that the biologically dewaxed petroleum product is heated for 1 to 10 hours at a temperature in the range of 250 to 370 ° c » and then separated into a light fraction »leaving the top of the column» which represents> · 70 to 97 »5% product fraction and in the heavy fraction» 4 part of the heavy fraction is reheated and returned either separately or together with the fresh deparaffinized petroleum product to the deatilaoe again. 2. A process according to claim 1, characterized in that the desired temperature and mean residence time of the petroleum product at this temperature as well as the desired degree of vapor conversion is achieved by controlling the ratio of the amount of fresh deparaffinized petroleum product to the amount of re-heated heated heavy product. 3. A process according to claim 1, characterized in that washing with an aqueous ammonia solution having a concentration of 2 to 20% by weight is carried out before the combined thermal distillation treatment. 4. The process of claim 1 wherein the lightweight fractionation is subjected to catalytic hydrotreating.