CS197641B1

CS197641B1 - Process for the separation of products from high-temperature pyrolysis of liquid hydrocarbons

Info

Publication number: CS197641B1
Application number: CS576777A
Authority: CS
Inventors: Bohumil Kral; Jozef Spacir; Stefan Camper; Ladislav Novak; Tomas Sebo; Stefan Benzir; Igor Borisek; Edmund Glevitzky
Original assignee: Bohumil Kral; Jozef Spacir; Stefan Camper; Ladislav Novak; Tomas Sebo; Stefan Benzir; Igor Borisek; Edmund Glevitzky
Priority date: 1977-09-05
Filing date: 1977-09-05
Publication date: 1980-05-30

Description

(54) Spfisob delenia produktov z vysokotepelnej pyrolýzy kvapalných uhlovodíkov(54) Method of separation of products from high-temperature pyrolysis of liquid hydrocarbons

Vynález rieši spfisob účinného delenia vodnej a organickej fázy pri vysokotepelnej pyrolýze kvapalných uhlovodíkov prídavkom komerčně a ekonomicky lahko dostupných látok.The present invention provides a method of efficiently separating the aqueous and organic phases in the high temperature pyrolysis of liquid hydrocarbons by adding commercially and economically readily available substances.

U doteraz známých systémov vysokotepelnej pyrolýzy napr. u systému vypracovaného firmou Hoechst, NSR, používá sa na delenie produktov pyrolýzy ahsorpčný deliaci systém. Jedným z uzlov tohoto deliaceho systému je.i solanko — benzínové pranie, ktoré slúži na vypranie Ca a vyšších uhlovodíkov a na vysušenie pyrolýzneho plynu. Ako solanka sa používajú vysokokoncentrované roztoky chloridbv alkalických kovov. Spfisob sušenia pyrolýzneho plynu koncentrovanými roztokmi etylénglykolu (ZSSR 1 692 511) je ekonomicky vel'ml náročný, nakolko proces vyžaduje číastočné odpúšfanie sušiaceho média. V solanko-benzínovom praní, kde pyrolýzny plyn sa dostává do styku so zmesou kvapalín solanka-benzín, vypierajú sa z něho rožne nečistoty do solanky, připadne do benzínu, ktoré spfisobujú vznik stabilného, disperzného systému až gelovitej konzistencie, ktorý bráni rozdeleniu fáz so1'ankou-benzín vo vařáku kolfiny. Na rozrážanie emulzi! voda — olej, čiastočne i na odvodnehie ropy sa používá oxyalkylovaný polyalkylénpolyamín, ktorý pre účely rozrazenia gelovitého systému je nevýhodný z dfivodu obsahu dusíka v molekule s možnósťou tvorby kysličníkov dusíka, resp. iných dusíkatých zlúčenín při pyrolýznom procese. Známe sú tiež deemulgátory používané na odvodnenie a odsolenie ropy, avšak systém solanko - benzínového prania je odlišný od uvedeného, pretože pracuje s koncentrovanými roz. tokmi hlavně chloridu vápenatého.In the prior art high-temperature pyrolysis systems, e.g. in a system developed by Hoechst, Germany, an absorption absorber system is used to divide pyrolysis products. One of the nodes of this separation system is also a brine-gasoline scrubber which serves to wash Ca and higher hydrocarbons and to dry the pyrolysis gas. Highly concentrated alkali metal chloride solutions are used as brine. The method of drying pyrolysis gas with concentrated ethylene glycol solutions (USSR 1,692,511) is economically demanding, since the process requires the partial drying of the drying medium. In brine-gasoline scrubbing, where the pyrolysis gas comes into contact with a brine-gasoline mixture, various impurities are washed into the brine or gasoline, which results in a stable, dispersive system up to a gel-like consistency that prevents phase separation. ankou-gasoline in the burner's burner. For breaking emulsions! Oxygenated polyalkylene polyamine is used in some cases also for oil dewatering, which is disadvantageous due to the nitrogen content of the molecule with the possibility of nitrogen oxides formation, resp. other nitrogen compounds in the pyrolysis process. Deemulsifiers used for dewatering and desalting of oil are also known, but the brine-petrol scrubbing system is different from the above because it works with concentrated solutions. flows mainly calcium chloride.

Podía tohoto vynálezu uskutečňuje sa spfisob delenia produktov z vysokotepelnej pyrolýzy kvapalných uhlovodíkov vypieranírti solankou a kvapalnými uhíovodíkmi, s odťahom plynných produktov a recyklom vodnéj fázy s odťahom kvapalných uhlovodíkov na štiepenie po rozdělení týchto fáz tak, že kvapalná fáza obsahujúca kvapalné uhlovodíky a solanku sa dělí pri teplote — 30 až + 30° C za přítomnosti látky všeobecného vzorcaAccording to the present invention, there is provided a process for separating high-temperature pyrolysis products of liquid hydrocarbons by washing with brine and liquid hydrocarbons, extracting the gaseous products and recycling the aqueous phase to extract the liquid hydrocarbons to split after separating these phases so that the liquid phase containing liquid hydrocarbons and - 30 to + 30 ° C in the presence of a compound of formula

R — O/PO/^x/EO/^yH kde R je alkyl s počtom atómov uhlíka 4 až 8, alebo skupina H/—- O — CH2 —/n, pričom n je celé číslo s hodnotou 1 až 6,R = O / PO / ^x / EO / ^y H wherein R is an alkyl having a carbon number of 4 to 8, or H / -O-CH 2 - / n, wherein n is an integer having a value of 1 to 6,

PO je skupina — CH2 — CH — O — ,PO is -CH 2 -CH-O-,

CHsCH

EO je skupina — CH2 — CH2 — O —, _x je celé číslo s hodnotou 15 až 31, y je celé číslo s hodnotou 1 až 6, v množstve 0,01 až 0,5 % hmot., počítané na vodnú fázu.EO is - CH 2 - CH 2 - O -, _x is an integer of 15 to 31, y is an integer of 1 to 6, in an amount of 0.01 to 0.5% by weight, calculated on the aqueous phase.

Postup podlá vynálezu je zámeraný na delenie produktov z vysokotepelnej pyrolýzy kvapalných uhlovodíkov, pričom pod pojmom vysokotepelná pyrolýza sa rozumie štiepiaci proces pri teplote nad 800° C, ktorý je v odbornej literatúre často označovaný a] ako HTP proces. Jedná sá o proces s prlamym odovzdávaním tepla z horenia do štiepenej látky. Surovinou používanou na štiepenlě šú kvapalné uhlovodíky různého zloženia, dodávané zo spracovania' ropy, pričom můžu byť bud širokými frakciami alebo destilačnýml rezmi, ·......The process of the invention is directed to the separation of products from high temperature pyrolysis of liquid hydrocarbons, the term high temperature pyrolysis refers to a cleavage process at a temperature above 800 ° C, which is often referred to in the literature as the HTP process. This is a process with a direct transfer of heat from the combustion to the split substance. The feedstock used for the digestion is liquid hydrocarbons of various compositions supplied from petroleum processing, which may be either wide fractions or distillation slices, ......

Híavnými produktamí pyrolýzy sá etylény a acetylén, ale okrem nich vzniká celá rada látok, ako například vodík, metán, kysličník uhličitý, kysličník uholnatý, uhlovodíky s nižším počtom atómov uhlíka, ako má východisková surovina kysličníky dusíka a zlúčeniny síry, Z hladiska technologického je potřebně vo velmi krátkom čase znížiť teplotu, aby _;sa zabránilo dalším deštrukčným reakciám, čo sa uskutočňuje olejml, na čo navazuje další stupeň, a to dochladzovanle pyrolýzneho plynu a jeho komprimácia.The pyrolysis products are ethylene and acetylene, but in addition there are a number of substances, such as hydrogen, methane, carbon dioxide, carbon monoxide, hydrocarbons having lower carbon numbers than the starting material, nitrogen oxides and sulfur compounds. in a very short time reduce the temperature to _; further destruction reactions are prevented, which is carried out by oil, followed by a further step, namely the cooling of the pyrolysis gas and its compression.

Po komprimácli sa pyrolýzne produkty vypierajú vo vodnej práčke, kde dochádza už k oddeleniu niektorých látok na'pr. aromátov, čiastoč_?ne kysličníkov dusíka, připadne vyšších uhlovodíkov. Parná fáza po tomto praní sa v dalšom stupni vypiera při teplote pod — 15° C, s výhodou pod — 20° C,, ochladenou solankou a uMo; vodíkovou surovinou pre štiepenie. Ako solanka sa používajú vysokokohcentrované roztoky chloridov alkalických koyov alebo alkalických zemin, najmá chloridu vápenatého alebo chloridu sodného. Solanka může byť upravovaná na určité pH napr. použitím HC1, alebo z hladiska korózie. Keďže solanka sa recirkuluje, obsahuje, vždy nějaké rozpuštěné alebo strhnuté látky z pyrolýzneho produktů á uhlovodíkovéj suroviny, ale obsahuje aj niektoré makromolekulárne látky, ktoré nepriaznivo ovplyvňujú delenie fáz solanka - uhlovodíková autoviha;' Obvykle periodický .'alebo .trvale; saí_; ťSakť- .sórartky odtahuje a nahradzuje čerstvou.-* ě; ; ' .After compression, the pyrolysis products are washed in a water scrubber, where some substances, for example, are separated. aromatics, partly _? not nitrogen oxides, possibly higher hydrocarbons. The steam phase thereafter is washed in a further step at a temperature below -15 ° C, preferably below -20 ° C, with cooled brine and µMo; hydrogen raw material for fission. Highly concentrated solutions of alkaline or alkaline-earth chlorides, in particular calcium chloride or sodium chloride, are used as brine. The brine can be adjusted to a certain pH e.g. using HCl or corrosion. As the brine is recirculated, it always contains some dissolved or entrained substances from the pyrolysis products and the hydrocarbon feedstock, but it also contains some macromolecular substances which adversely affect the separation of the brine-hydrocarbon fuel phases; Usually periodic or permanent; saí _; The "bag" withdraws and replaces fresh. ; '.

.·, Pri, vypieraní a.íjdqlept.fáz sa jdo.stávajú do uhlqvOdíkovej .syroyiny_i;.aj.,in.é Jýtky, ktoré . v nej. půvoáne nebdiil· Pjfědqvpetikýip., dochádza k stavu biížRějňú? róýixqvážnemy. stavy,: alebo rovnová?němu šťávu rtieďží. ;uhlovodíkovou' surovinou a paritou fázdu,.po vypieřání vodou a solankou,, ďalej' k přestupu ‘piektorých¹ 'íátýk medzi solankou a uhlovodíkovou surovinpújyhajma pri delení fáz. -Vplyvom různých látok pri delení fáz dochádza k vytvorenlu disperzného systémy až, gelovitej konzistencie/ , čo sa . negativné odráža na znečistění uhlovodíkovéj suroviny s bezprostředným dopadorii ria životnost zariadenia a dodržovanie technologických podmienok. Spravidla klesá výkonnost zariadenia s priamymi statami vo výrobě. · ·In the course of the washing and the other phases, they become into the carbonaceous carbon _; .aj., et al. inside her. initially not watching · Pjfědqvpetikýip. róýixqvážnemy. states, or equilibrium juice of the juices. , the hydrocarbon raw material and parity fázdu, .po elution with water and brine ,, hereinafter 'the transfer' piektorých ¹ 'íátýk the brine, hydrocarbon surovinpújyhajma in the separation phase. Due to various substances in phase separation, dispersion systems are formed up to a gel-like consistency, which is achieved. it negatively reflects the contamination of the hydrocarbonaceous feedstock with immediate dopadorium and the service life of the equipment and compliance with technological conditions. As a rule, the performance of equipment with direct states in production decreases. · ·

Ak sa do prúdu solanky, alebo do děličky pri delení fáz do systému prldajú látky všeobecného vzorca R — O/PO_x/EO/j, dochádza k rozrazeniu disperzného systému v. technologicky požadovanom čase, ktorý zabezpečuje.kontinuálny proces. Látkami uvedeného typu sú rožne própox— a etóxamery nižších alkóholov komerčně dostupné na trhu ako propox-etoxamer butanolu (butoxislovaníky), propox-etoxamer 2retyl-hexanolu, ale aj propoxamer etoxy.loyan.ý sl.až 6 molekulami etylénoxidu· na ,koncových funkčných skupinách (slovaniky) a iné obdobné,;látky zodpovedajúce všeobecnému vzorců.-Přidávané množstvá počítá-né na vodnú fázu sa spravidla pohybuje v rozmedzí 0,01 % až 0,5 hmot. Q/p, pričom z hladiska technologického spravidla postačuje už množstvo 0,01 hmot. %, čo je velmi priaznivé aj z ekonomického hladiska.When substances of the general formula R - O / PO _x / EO / j are added to the brine stream or to the separator during phase separation, the dispersion system in the. technologically required time, which ensures the continuous process. Substances of this type are various propoxy and ethoxamers of lower alkanols commercially available as propoxy-etoxamer butanol (butoxisyls), propoxy-etoxamer 2-ethylhexanol, but also propoxamer ethoxyloyed with up to 6 molecules of ethylene oxide. The amounts added, calculated on the aqueous phase, are generally in the range of 0.01% to 0.5% by weight. Q / p, with a quantity of 0.01 wt. %, which is very favorable also from the economic point of view.

Medzi hlavně výhody postupu podía vynálezu možno zařádit skuťočnosf, že nepriek látkové velmi různorodému systému za přítomnosti vodnej fáze s vysokou koncentráciou minerálnych látok sa podařilo jednoduchým přidáním aj komerčně dostupných látok rozdělit .djeperzriý systém, pričom přidávané množstvo látky prakticky neovplyvňuje ekonomikuprocesu. a přidávaná látka ani negativné nevplýva na proces pyrolýzneho štiepenia.Among the advantages of the process according to the invention are the fact that, despite the highly diverse system in the presence of an aqueous phase with a high concentration of minerals, the dispersive system has been separated by simple addition of commercially available substances, and the added amount practically does not affect the economics. and the added substance does not negatively affect the pyrolysis cleavage process.

Příklad 1 kg detergentů etoxylov.aného polypropylénglykolu 1200 (obsah polypropylénglykolu 90 % hmot., molekulová hmotnost 1200 a 10 % hmot., etylénoxidu) obchodný názov SLOVANEK T 310 sa zmieša s 10 m³ čerstvej solanky (33 % roztok chloridu vápenatého) a v priebehu 10 až 12 hodin sa zmes dávkuje do 40 m³ cirkulujúceho znečistěného roztoku solanky v prevádzkovom systéme.Example 1 kg of detergents of ethoxylated polypropylene glycol 1200 (polypropylene glycol content 90% by weight, 1200 and 10% by weight, ethylene oxide) Trade name SLOVANEK T 310 is mixed with 10 m ^{3 of} fresh brine (33% calcium chloride solution) and during The mixture is dosed into 40 m ^{3 of the} circulating contaminated brine solution in the operating system for 10-12 hours.

Po dvoch hodinách důjde k rozrazeniu disperzného: gelovitého systému, k oddelovaniu lahkého benzínu od solanky a k stabilizácii technologie-, kého režimu.After two hours, the dispersion: gel-like system breaks down, separates the light gasoline from the brine, and stabilizes the technology regime.

Příklad 2 kg detergentů ako v příklade 1 sa pomocou dózovacieho čerpadla nadávkuje do znečistěného cirkulujúceho roztoku solanky (obsah 40 m³).Example 2 kg of detergents as in Example 1 are dosed by means of a dosing pump into a contaminated circulating brine solution (40 m ³ content).

Po cca 0,5 hodině důjde podobné ako v příklade 1 k rozrážaniu disperzného systému, k oddelovaniu lahkého benzínu a k stabilizácii technologického režimu. ^v'After about 0.5 hours, a dispersion system is precipitated, separation of light gasoline and stabilization of the process regime similar to Example 1. ⁱⁿ '

Příklad 3 . .0,01 % roztok detergentu butoxylovaný polypropylénglykolmonobutyléter (mol. hmotnost, polypropylénglykolmo.nobutyléteru je 1814 a v moíěkuíe je 10 % polyétylénoxidovej zložky) obchqdný názov BUTOXISLOVANIK BK 61 sa spolu, s čerstvou solankou privádza do cirkulačného solánkového okruhu, čím sa dosiahne stabilizácia prevádzkového uzla a zníženie množstva pridávanej čerstvej solanky na 0,5 m³/hod, oproti 0,& m³ solanky/hod. pridávánej bez detergentů,Example 3. A detergent solution of butoxylated butylated polypropylene glycol monobutyl ether (molar mass, polypropylene glycol monobutyl ether is 1814 and possibly 10% polyethylene oxide component), commercially named BUTOXISLOVANIK BK 61, together with the fresh brine, is fed into the circulating brine circuit to reach a circulating brine circuit. and reducing the amount of fresh brine added to 0.5 m ³ / h, as opposed to 0 & m ^{3 of} brine / h. added without detergents,

Claims

referred to as] an HTP process. It is a process with a heat transfer from the burning of the split material. The raw material used for the cleavage of liquid hydrocarbons is a rhodium composition obtained from the processing of the oil, and may be a wide fraction or distillation section. Thin pyrolysis products are ethylene and acetylene but, in addition, a number of substances are formed, such as hydrogen, methane, carbon dioxide, carbon monoxide, hydrocarbon lower carbon atoms, such as starting nitrogen oxides and sulfur compounds. It is necessary to reduce the temperature in a very short time to avoid further raucous reactions, which is carried out by oils, followed by a further step, namely the cooling of the pyrolysis gas and its compression. After compression, the pyrolysis products are washed in a water scrubber where some substances are separated into the water scrubber. aromatics, partly nitrogen oxides, possibly higher hydrocarbons. The steam phase after this washing is subsequently washed at a temperature below -15 ° C, preferably below -20 ° C, with cooled brine and with carbon, hydrogen feed for cleavage. The saline solutions used are concentrated alkali metal or alkali metal chlorides, especially calcium chloride or chloride solutions. Brine guns are adjusted to a certain pH. using HCl, or for corrosion. Since the brine is recirculated, it always contains some dissolved or entrapped substances of the pyrolysis product and the hydrocarbon feedstock, but it also contains some macromolecular substances that adversely affect the phase separation of the so-called hydrocarbon aurovha; Usually, the periostatic or permanent drug is withdrawn and replaced by fresh silane. In particular, the calf, or the juice of the same weight, is hydrocarbonaceous, and the vapor phase, after the water and brine has been wound up. Due to the various substances involved in the phase separation, a dispersion system is formed up to a gel-like consistency, which is negatively reflected in the contamination of the hydrocarbon feedstock with In the meantime, the lifetime of the equipment and the adherence to the technological conditions are generally reduced. The general formula R-O / POx / EO / j results in a dispersion-dispersing system in a technologically desirable time to ensure a continuous process. Substances of the type mentioned are spheroids of lower alcohols commercially available as propoxethoxamer butanol (butoxy- the propoxy-ethoxamer 2-ethylhexanol, but also propoxamer ethoxylated with 6 ethylene oxide molecules at the end-functional groups (slavics) and the like, corresponding to the general formulas. Typically, the aqueous phase is in the range of 0.01% to 0.5% by weight. Q / p, with 0.01 wt. %, which is also very favorable from an economic perspective. In particular, the advantages of the process according to the invention can be characterized by the fact that a large variety of systems in the presence of an aqueous phase with a high mineral concentration has been successfully separated by commercially available substances to separate the system, with practically no effect on the process. and the addition or the negative does not affect the pyrolysis cleavage process. Example 1 70 kg of ethoxylated polypropylene glycol 1200 detergent (polypropylene glycol content 90 wt.%, Molecular weight 1200 and 10 wt.% Ethylene oxide) The trade name SLOVANEK T 310 is mixed with 10 m 3 of fresh brine (33% calcium chloride solution) and over 10 hours. up to 12 hours, the mixture is metered into 40 m 3 of circulating contaminated brine solution in the process system. After hours, the dispersion gel system breaks down, separating the light benzine from the brine and stabilizing the technology mode. EXAMPLE 2 50 kg of a detergent as in Example 1 is metered into a soiled contaminant of a circulating brine solution (40 m3) by means of a scrubbing pump. After about 0.5 hour, the dispersion system is similar to the one described in Example 1, to remove light gasoline and to stabilize the technological mode. v 'Example 3. 0.01% detergent solution butoxylated polypropylene glycol monobutyl ether (mole weight, polypropylene glycol butyl ether is 1814, and the molecule is a 10% polyethylene oxide component, the common name BUTOXISLOVANIK BK 61 is fed together with the fresh brine to the circulating vessel circuit to achieve operational stabilization) node and reducing the amount of added fresh brine to 0.5 m 3 / hr, versus 0.6 m 3 golan / hr added without detergent, SUMMARY OF THE INVENTION A method of separating high-temperature pyrolysis products from liquid hydrocarbons with scrubbing and liquid hydrocarbons, with the exhaust gas and the recycle of the aqueous phase with the removal of liquid hydrocarbons for cleavage of the phases, characterized in that the liquid phase containing the liquid hydrocarbons and brine is separated at a temperature of -30 to + 30 ° C in the presence of a general formula ... R - Ο / ΡόΛ / ΕΟΛΗ where R is alkyl having carbon numbers or 4/8, or a group H / - O - CH 2 - CH 2 / ", wherein" a bar number of 1 to 6, PO is a group - CH 2 - CH - O -, I CH 2 EO is a group - CH a - CH a - O -, x is an integer of 15 to 31, 3 / is an integer of 1 to 6, in an amount of 0.01 to 0.5% by weight, calculated on the aqueous phase.