DE1545335A1 - Additive to reduce pollution when refining petroleum products - Google Patents

Description

Applicant: NAICO CHErtlCAIr COMPANY, 6216 West 68th. Placa, Chicago XtI. Y.St + k *

Additive to reduce pollution beia Refining of petroleum products.

The invention relates to improvements in processing or Haffinieren of hydrocarbons »and sio looks at inebesondare to chamieche additives for noroalerveis Liquid or ready-to-use Beschiciniasagut used to manufacture finished hydrocarbon products.

Eb is allgenein common chemioohe Zusatsstoffe tu finished Er4i (I-Koliienwasserstoff product s, such as gasolines, Xeroainen, Brenniilaa, finished Löeungsnitteln xususetsen like. To get engaged yew among others these products desired properties and obtaining * iieitBBierkmale. In modern working methods

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BAD ORfGWAL

numerous hydrocarbons are used as feed material »the links in the manufacture of pavers Products are. Until recently, little attention was paid to the properties of this load, as it was quickly guided through the processing plant, where it has been converted into substances whose physical and chemical properties are different from those of the starting material. were divorced.

Due to the growing economic importance of the petrο-chemical industry and the steadily increasing demand for Gasoline with a higher octane number, improved lilac gasoline and better residual fuels, one went over to the different types of feed to the refineries treat it to extract better fuel values or to convert it into useful and valuable petrochemicals. Significant amounts occurred through these various procedures Problem · when editing on «which was not previously critical 04.

One of the most unpleasant phenomena in treatment of various hydrocarbon feed stocks that is now recognized and labeled as pollution Phenomenon. It manifests itself in deposits that are often deposited on the metal surfaces of the processing system and tend to compromise the performance of interim workers

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The immediate results of pollution occur in the form of heat transfers Losses, increased pressure drop, loss in throughput on, and in some cases there is a special kind of corrosion ^ - Observe product that along with the deposits accrues

The loads that cause pollution in the back-up systems of the Baffinerie include naphthas * gasöje, roboils and petroleum gases. The naphthas or light residues can be referred to as light oils and usually have a boiling point in the range of 32 ° - 60 ° O (93 »500 ° F). The gas oils are intermediates between the so-called kerosene fractions and light scavenger oil diluents and generally distill between 27 ° and 399 ° O (520 ° and 750 ° F). These gaa oils are commonly used as a feed to cracking plants, where the molecules are broken down into smaller components. The crudes that aeietene are the cause of pollution, are unused J products that are introduced into the first refining step and include all petroleum fractions _t normally removed in the refining * The raw materials used for the present invention purposes include the so-called. Residue or Kessell Actions left after removal of the volatile and solvent extractable components.

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BADORfGINAL ....

Other hydrocarbons that may be treated according to the invention aind _t Petroleuagase or normally gaseous alkane and Alkenkohl enwasserstoffe ·. which usually boil between -157 ° and 38 ° C (-250 ° and Ί0Ο ° P). This subheading includes methane, ethane and propane. Butane, ethylene, propylene etc ... These hydrocarbons can be present in the liquefied or gaseous state during the treatment according to the invention. These normally gaseous substances can be liquefied when subjected to superatmospheric pressures or low temperatures.

The various loads identified above are often subjected to one or more of the following general heat or heat subjected to catalytic processes to produce fuels? Reforming, cracking, alkylating, ionizing, Polymerizing, desulfurizing, hydrogenating and dehydrating. Bieet various procedures and their codifications are described in the publication: 'Petroleum Refiner, September 1962 ",

Similar problems arise in plants in the petrochemical industry where the hydrocarbon charges are often heated at normal or elevated pressures. For example, in the division of acetylene using the BASF process, light naphtha or natural gas is preheated with oxygen before partial combustion in order to form acetylene and other by-products.

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Production processes are hydrocarbons, such as naphthas, subjected to thermal cracking. In the alkylation of aromatic substances, benzene or other aromatic hydrocarbons are mixed with a gas containing oil, heated to alkylation temperature and converted in the reactors Hydrocarbon gas, liquid hydrocarbon or the like. mixed with steam, the G _e v mixing preheated and formed in a reactor, a gas consisting mainly of carbon monoxide and hydrogen, the latter being implemented in a process stage späeteren with nitrogen / ird. Benzene and hydrogen are reacted in systems with heat exchangers to form cyclohexanes. "Light hydrocarbons, monoolefins and their mixtures are heated before catalytic dehydrogenation into monoolefins and di-olefins." Ethylene feed is pressurized before reaction with water to form ethanol heated ο Light and heavy crude oils or crude oil fractions are preheated in ethylene and propylene and C ₄ -01efin before thermal cracking. In the hydro-alkylation of lower] aromatic alkyl compounds into simple aromatic compounds and gas, the lower aromatic alkyl precursors are mixed with hydrogen and preheated before the hydro-dealkylation.

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These are examples of petrochemical processes in which, among other things, "a" the method according to the invention for reducing the formation of deposits on heat exchange surfaces from hydrocarbons * Other petrochemical processes, for which the additive and the method according to the invention are suitable are in the "Petroehemischen Handbuch" published by "Hydrocarbon Processing and Petroleum Refiner" find atf. The last release is in volume. 42, No. 11, page 129 ff »November 1963 (GuIf Publishing Co,) appearedο

The mentioned deposits occur most frequently on heat exchange surfaces at elevated temperatures between 37 ° and 1093 ° 0 (100 ° and 2000 ° P), in particular between 93 ° and ■ i 593 ° Ο (200 ° and 2000 ° F). The mechanical systems usually attacked are heat exchangers, heaters, condensers or »coolers, compressors and auxiliary systems. Catalyst beds can also be seriously fouled by these deposits. In the case of mechanical systems, the load is usually passed through various types of heat treatment systems, such as pipelines, Heat exchange type ovens and the like for Hessen * For the sake of simplicity these systems are referred to as lines in the following.

The deposits formed on the heat exchange surfaces, for example metal surfaces, are in their composition anyway

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different and can be organic, inorganic or mixed organic and inorganic compounds. the Organic precipitates are mainly products of polymerization and are usually black rubbery hates that Turned into coke-like hates at elevated temperatures can be. The inorganic parts of the deposits often contain components such as silica, iron oxide, sulfur trioxide, iron sulfide calcium oxide, magnesium oxide, inorganic Chlorides, Sodium Oxide, Aluminum Oxide, Sodium Sulphate, Copper ^ oxides and Copper Salts- It is difficult in the ones Operations locate the source of the inorganic components of the precipitates and deposits see below, but often they probably come from the ash content of the crude oils, from corrosion * products of the metal surfaces »with which the load comes into contact and of contamination by the Contact with various metallic catalysts that are used to process the goods.

The problems mentioned are of a different nature than the known ones Appearances of corrosion and sludge formation, which often occur in finished products The digested sludge or sediment formation in finished products has no relation to eu Pollution, since deposits of the first-mentioned type through Organic solvents, such as benzene, acetone and the like, can be made easily soluble within the scope of the invention the deposits in question known as Vereeliimtsüng

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Deposits designated can be caused by usual organic Solvents cannot be easily made soluble · The inorganic deposits, which act as pollution products are often more complex in their structure than the homely erosion products and are therefore easily under * divisible.

When the pollution was recognized for the first time, it was believed that they can be corrected by doing known means preventing oxidation or stabilizers in this way to eliminate the problem. But it appears soon that such additives, so common petroleum * b * w. Petroleum additives, are relatively ineffectiveSs is therefore a real need to combat the problems mentioned, and awar through economical chemical additives that im Relatively low levels are effective. This task is due to the inventive additive * and the process been solved.

Oils experience in its simplest form relates to a petroleum refining process for the production of liquid and gaseous hydrocarbons or hydrocarbon processing * Tunga process for the manufacture of petrochemical products and Hydrocarbon products in which a hydrocarbon with an exchange surface, such as a metal line comes into contact with η, and awar under temperature * and bridge * conditions that result in the formation of deposits on the surfaces

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of the heat exchanger cause »ITa prevent such deposits or contamination xu, a former additive is added to the work process Mix well · It has been found that this works certain H-alkylamido phosphoric acids are suitable, which are described below listed child:

(A) HO-P-H

OH

* Ic

-I-

OH

r ί 0-P-

HRR T 1 2 j

R ₆ O

HR ₁ R ₂

-I-

I. ÖH

0 I.

R ₆ OP - HR ₁ R ₂

In the _6th

Fr ₆ OP-OI FhHR ₃ R ₄ R ₅ J HR ₁ R ₂ ^J

00 OO fl HA I

R ₂ R ₁ HPOPOPO-P -HR ₁ R ₂

1 i \ I

O HR ₁ R ₂ OO

909884/1593

and their mixtures, above which R ₁ , R ₂ * R * »R41 are Re and RgRtate, such as hydrogen, alkyl, alkenyl, alkaryl, aryl, cycloaliphatic radicals, Qycloheteryl, these radicals have subatituents, in at least one of the radicals mentioned 8 carbon atoms are present »

The compounds on the sole can be synthesized by various methods. The precautionary method of preparation, however, consists in the successive reaction of τοη phosphorus pentoxide with a primary or secondary ^Ag i1n and pti - finally with an alcohol. After this synthesis, a mixture of substances listed under A, 0 and £ is formed. In order to produce the compounds B, 0 and F, the compounds A and D are neutralized, the salts of amidophosphates being obtained. The last compound, namely G, is best prepared by reacting phosphorus pentoxide with a primary or secondary amine in a certain ratio of 1: 6 from phosphorus to amine «

The formation of the aforementioned class of amidophosphoric acid compounds can be achieved by a large number of reactants be used. As already mentioned, is phosphorus pentoxide a preventive phosphorus-containing reactant · But many other phosphorus-containing acid compounds can also be used, so i.B. Phosphoric acid · phosphorus oxychloride, phosphoric anhydride and the like.

BAD ORIGINAL 9 0 9 8 8 A / 1 5 9 3

Pas Arnin. can be either a primary or a secondary amine sola, which has at least one reactive hydrogen atom has to form the corresponding amido group ^ Hs it was found that in at least one case the primary «) or the secondary American» one of the above mentioned haste should contain at least θ carbon atoms · substance « of this type have outstanding corrosion-inhibiting properties < if they are too normally fluid to edit or to stored hydrocarbon stocks are given _c by-

• ι

games of amines, which are used for the production of the erfindungaeemäss

compounds used, are _t are given below. These substances can be used via a first reaction with a phosphorus-containing acid, upon which

Reaction with an alcohol follows in order _{to form the compounds A f} and E , from which by neutralizing dl corresponding salts can easily be synthesized. They can also be reacted with a phosphorus-containing acid to form the compound Gr

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Table I.

1 «n-dodecylamine

2. n «tetradecylamine

3. n ~ hexadecyl arain

4. Laurylaain 5 ^ Hyrietylamln 6. Palmitylamia 7 stearylaain 6. Oleylamine

9. KolcoBGusacla-oin 10 "Tallow amine

11. Hydrogenated TaXgamln

12. BausnrolIaamenöXamin

13th

Dilaurylamia

13iiayristtlamin

Sipalmitylaral »

16. 1? "

1Θ,

19 »20. 21 π 22. 23 · Dilorylamine (Dlooconut) dihytiriertee Talgun in Octylnethy) amine Octadecylmothylamin Outa & euylbettssylanln Hoxyläthylanin Soyaauin (Hexadecyl-10% _t Octadecyl-10% Octadecenyx-45 / j)) Octadocadiene

A particularly preferred class of amine HeaktioreteiXnehaem and higher alkyl-substituted imidazolines, boi-gameselee those of the general formulas:

(H ₁ NH)

E-c:

Formula ^ , XII y S93 ., N - ORfGlNAL I.
R ₂ · # - * «Μβ-ϊ" ^ Q wmer »,
f
H
9098 -H - Z
84/1 BATH

where H is an aliphatic group with 1 - 22 carbon atoms in the chain length , Ϊ and Z is hydrogen or a lower aliphatic carbon atom group with not more than 6 carbon atoms in the chain from H or hydrogen and η is an integer from 1-50. · Imidazolines with the formula ΐ, Ll and XXI are conveniently made by reacting a monocarboxylic acid, such as a saturated or unsaturated fatty acid, with an A.'kyJenpoljaioin or Hrdroxy- »alkylalky The imidazolines formed can be converted further by 0xya3 icy) leren _; ium "to win other suitable derivatives procedures are in" The Chemistry of the Imidazolines and Imidac.lines' by RJ Ferm and JL, Riebaoaer, Cnemical Reviews Volume 5i4, no. 4, August 1954 described for producing these Imidazol.iuen Att Particularly suitable imidazolines for the purposes according to the invention are the compounds known from US Pat ) -2-tal.lölimidazol ^ jQ, both of which can easily be prepared by the process according to the USA patent 2 267 965,

The following are examples of such imidazolines:

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· »- (2" Hydxo3 ^ äthy λ) "2-tridecyliaidazoliu, ~ (2-Hydxo2Qrä fehyl 3 -2 -pentadecyliaidazo.lin - C 2» Hydroagräthy.i) »2 -heptadecylitaidassol in \ - ν 2-Aniinoäthyl) - 2 ~ heptadecy limidazolin ι- Q2-AoinoäthyX) ~ aminoethyl 1J - ^ - undecylimidaaolJ.n, - jl (2-Arainoäthy: 0 »AminoäthyI j

The fatty acids have generally been reacted with a PolyaJkyJarpolyamin, such as Dj.äthylentriaioin, Iriätnylentatremin, LetrR-Ethylenpentaxiin or other mixtures, or a Polyamine alcohol, such as Aminoäthyläthanolamin. The AKAn-3eak · - nationals can also use lower alkyl groups be substituted.

A particularly preferred class of Aain reactants are! tertiary alkyl primary amines. These have the general formula

0 -

More precisely, di · tertiary alkyl primary amine · are compound ·! in which R ^ and Rg are lower alkyl groups, ordinary methyl groups, and 3 »a long-chain acy |, reat consisting of 8-19 carbon atoms, tertiary aiiy3 primary amines, which are extremely suitable for the purposes of the invention, si.n4 those under the. Hamen "Primen" 31 -ft ^! And

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"Priraane JTi-T" known products, Ee is stated that the "Primene 81-R" consists mainly of tertiary alkyl primary amines of 11-14 carbon atoms and a molecular weight essentially in the range of 171-213 and one s specific gravity at 25 ° C of 0.813, a refractive index at 25 ° ^C of 1.423 and o3n Neut.raliBatiousfiquivö.len; of 191. The indications of "Primene JW-T" are tertiary «Alkjl primary Αηύηβ with 18 ~ 2 ? Carbon atoms, molecular weight i »essentially in the range of 269 - 325 · specific weight at 25 ° 0 of 1,4,56 and a neutralization equivalent ent of 515 ·

The essential part of ^M Primene 8 '<~ R ⁿ soli

CH ₃

1 ii

H, ö - G - OH «0 - -GHo - 0

3 d <i

, d , <ij 2

The main component of "Priaene JW-T ^r should have essentially the same structure as that of" Prinene-81-R ", but only 22 carbon atoms.

The alcoholic reactionaries can also from a Groasen anssahl of alcohols «Msgeaucht, berorsugt but are primary and secondary * »alcohols. This alcohol · have Residues corresponding to the compounds listed.

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Examples of such alcohol compounds are normal straight

fatty alcohols, such as ethyl, n "propyX, η-butyl, n-alayl", n-hexyX- _t n ~ hepty ~ _f n ~ Qctyl ~, n = Noayl-, n-decyl, 2i "indecyX n ~ Bodecyl ~ (LruryJ), n-TetradecyX ~ (tfyrietyl ») _t n-Hexadecyl (Getyi ~), and. n ^ Octidecyl-, stearyl-}; \ Lkohol»

primary alcohols with branched chains »such as

Isoamyl-, 2 ₁ 2, ^^ iiaethyl- '' i-hexanol and 5,?,:

2- (1.513 "-trimethy! Butyl) -Λ -octauaoi j

and secondary alcohols? like leopropylaXkohol »sec-ButyXaXkolt & 2-pentanol, 2-octanol, "i-methyl-2" pentanol and 2,4-dimethyA-3-pentanol,

An example of alien alcohols are cyclopentanols
QycXohexanolt Oyclopehtanol and Methol _e

Examples of ethylenically unsaturated alcohols are allyl,
Crotyl, oleyl, <cis «9-ocitadeceii-1-ol) _s citronellol and
Geraniol

Acet; ylenically unsaturated is, for example, propargyl alcohol, araliphatic?) Alcohols are benzyl, 2-phenylethanol _t
Hydrocinamyl and A], pha ° methyl-> benzyl alcohols _e cinnamyl alcohol is an example of an alcohol that has both aromatic and ethylene unsaturation.

An excellent source of alcohol are the als
Oxo alcohols known compounds * These are normal »

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wise a mixture of alcohols with different chirps = molejculargewichfcen, which have 4 to about 16 carbon atoms. Their preparation and Indikatilonen are in the book "Hißfcer Oxo Alcohols" L ₀ F * Hatch, Enjay Gonpany ,, Ine "1957 be" sehriebim "koliole The general composition of i / and Sster-STöbanprodukte _t eiaea oxo alcohol ~ represent the \ m straws of the invention can be used, is the following?

component

it on

-so- and a -oetylal ^ kchol i - '2O

Xao- and n-Nc-aylai- alcohol 5 - .- ^

S ^ ^ 30- and ηUecyl and

hiixevo alcohol 25-90

typical Desti.vlierboden-O ^ o-Aiöcoiiol, which siöh ausbei the preparation of the N-alkylamido-phosphoric acid compounds Suitable according to the invention has the following composition:

Component . Weight percent

C _e alcohols 5

Gg alcohols 10

0 ^ ₀ and higher alcohols 33

Ester 45

Soaps ■■ 5

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«18«

How ready are mentioned above by the three ormaln A ₅ £ and E shown Connectivity ¹ mg en easily by reacting eii;? ^ · Phosphorus-containing acid \ ιη.ά an amine and succeed! ■ * ? Haaktion with e: U '". Em der obei?, 3" called alcohols hergaafctiXXt ,. The saichnefcen connection through the Feraei & gekc-.r. '.' are through ümsetae ^. difference. 'aar Hangen Atixx -ναχΐ p.ios.jff.or-containing acid alXoin j. ^ ^; I.-det "The degree, bia 3u we ^ c.?. ··. 5. ⁴ , ns Riosphorviirbiniung, wi. j / hesph ^ rper ^ o ^ iä, αηί1-3τ? ϊ w5.rd, depends on the number of excesses. Mo_e Aoin _t dJ.o per mole of phosphorus compound / erwendefc werdeiii from "A ratio of 6: · '· Aain au I ^ t ^ phorverbindung ejcg..bfc a fully amidiertea and βία completely neutralized product, ^daa: Aiaidgruppen iM 5 Ssitzgruppen DEFAULTS. Dur- ;: Varying the ratio, partially or completely neutralized tferfcinduagan can be formed «

Connections according to the lavmeJjo. B, Q ui; d Έ to gain the connections A imr ⁵ , D Sedig ^ ish neutralized by adding Äiain ^ earth. > The neutralization aai.iie can from the already described group of amines or? the one of the connections listed in the following labels ^ 11 must be selected.

StiSS & S-S

1. Ethylamine

2. Diethylamine
3 · morpholine

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BATH ORIGINAL.

: 5 4 5 3 3

19 Continuation of CabeUe TI

4. Bufeylamine

5. Isopropylarain o. diiaopropylamine .?., N-Methylmorpnoiir. β ο Irläthyläjnii?

9 ο AminoäthyXäthanoliaiain 10τ jüiätij.ano? .Amia 11., I'iethyXäthaiiolamin

¹ 12. Diiaopropanol amln I? Dimethyl ethanolamine 1if. Dimethyl iaopropauolaini, n 15. N-HydrojQratshyimorpho 16- .N-Methyidiäthajiolamln 1? O Monoathaaoiaaiin 1Θ. Monoiaopropai ^ iamin

19.! Triethottolamln

20, Triiaopi? Opan.ctam ±: a

? .2o -i ^ -dihydrojir / iaethyl n-propylainin 3, Polys4ykol, amia'K ₂ NCSH-CH ₂ -OCHgCH ^ OH; * f », PyrroUrlou

Inidaaol H.

I 28 Polyemiae der KXacse H ₂ N (^ RN) ₃ K, where fi is a A3kyle * n-

^like -CM ₂ CH ₂ -. or

-CiI ₂ CH ₂ CW ₂ - or

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Table II continued

H 2

σ
ι

if UD.d 3t is an integer from 1-5 means -29 »5-bancimidazoi 3JOο 2 - Hydroxy & thy] timidazo! 3 "U 2 - methylini.iaazole 32. Pyraüin 33 “Pyridine 34 "Piperidine

.55 "2-Cyanomethyi -2-inidaÄoIin 36 c CyclohexyJamine

The following examples explain typical «* ^ experienced for Distribution of the additives used according to the invention (antifouiante).

example 1

In a eauberen, with dry nitrogen fogged 376.5 1 (100 gall) comprehensive Beaktionskessel stainless steel t equipped with a stirrer and a water-cooled steam-heated jacket, were 58,2o kg (130.5 lbs) kerosene and 27 »22 kg [6o _t 0 lbs) was added Fhosphorpantoxid "These reactants were rascb durcheinandergorührt, to form a Aiifscblämmung, in that Phosphorpentojcid

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was suspended in the form of fine particles. 18.24 kg ("^ 0.2 Iba) of the product known under the name" Frimene 81-Ji "were slowly added to this dispersion so chosen and. maintainso / j. «that a temperature of 10 ° ^f) C was not exceeded © - The reaction mixture was then atoned for 1 - 1 * 2 hours at 100 ° C, whereby, during the whole process, a nitrogen atmosphere was maintained, and this preferably, prints slightly above atmospheric pressure were "After DEI period called the Reaktionasemisch to 40 ° Q was cooled and 62.37 k £ (137 * 5 Ib8 / laooctanoi slowly ssugegebano this was dia temperature to 40 - 5C ° G _t, if necessary by cooling, kept awake the lao octanoi addition was, the mixture was 2 -. ^ Z hours at 100 ° - 150 ° Q held After this time the solution was clear..

The compounds formed corresponded to the formulas A, D and E, where H _{1 is} hydrogen> R _{2 is the} following radical

CH, CH, CH,

! * I ⁵ 1 ⁵

CH - 0 - CfH ₉ - 0 - "I ² I ² I

CH ₅ CH ₃ Cffj

«M Hg were an isooctyl radical. The products were roughly the same proportions formed, as was determined by potentiometric titration, and they could through Usual methods, such as extraction by solvents or the like. be separated. The substances could be in the form of a mixture

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used as they are all in different degrees as Corrosion inhibitors are effective * The actual ratio of P ^ O ^ q: Aoin: alcohol is 1: 1s 5 »

Eg a mixture of Ve ^ biMurgen was measured. ^? onae. B and D by «ailwsisos Keutralisi iv- ^ i the mixture of IT-alkyl amiaophosphoric acids according to 3ei £ ipiei * bsrgestal ^ v - -in case- became ils Neutra ^ ioati-ν: .. 8νΐ1ΐ1.3ΐ Ia3 xantfir the" Primec.e SI-R "-Amin use ':.

In this experiment the completely neutral salts of Gamiachea see K- »Aj £ 5r;, amidophospho3satiren seaasa Example 1 were obtained. Also here was the neutral agent, the product known ^{under the name K} Priaene 8 ^ -H ^{! 1.} It binds, the ponae ^ ii E and F won

J2s were d: le ßeaktionstel ^ ehiier according to B ^ ispid ". 1 veremlet, with the Ausaabjaej that the ratio of ~ ^^ _ίΛ ? Aain: alcohol s2" ^e i ^ua "<* 2 s 4, Bas er * ial5" The mixture of substances corresponded to that from Example 1, but the relationship between the two substances varied.

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Here, too, the reactants according to Example 1 were used, but the ratio 1: 1: 5 * 5 was chosen. The products were then completely neutralized using the amino known under the name "Primener 81-R ^r,"

Example 6

Be * This test was carried out a synthesis, were used bsi only P ₄ P ^ Q and Aoin and particularly that known by the sculpting "priming" 81-R "Product · Here, the compound of BOraiel G was prepared, in which K _1, Rg ♦ H ₃ ,, R ^ and R ^ best derived from the amine reactant. The molar If never goes from AMn to P ^ O ^^ was 6: ''.

The procedure according to Example 1 was modified to the effect “dasF. Instead of `` Prlraene 81-R ⁿ a iiaidazoline was used. This was produced by reacting Am.inoath.yi.- »ethanolanu, n aiii a mixture of heptadecuyl and heptadecadlei3yJ, fetbßiuren * The lao.lare ratio The three participants in the action was again Λ i Λ r '> _ν 5 and the product was 50 $ active in kerosene.

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BADORIQINAL

Example 8

There were keeping exactly the YerfahrenBschritte contemporary example is i _t but in this case the final product was 50 # Aktivea in kerosene "

Srcuukt c? ⁽ⁱ iäss Böi.splel "i W: L» xle iie. ^ i.est ^ '■ H _f ate * - JL ". 0% aktr.Vi'-r Fu / ^ i in Ki

A view of other substances contained in the Btrfi ^ t. .Fre- £ χ · ~ discovery were made with other amines ^ a, A2, koho ^ m ,, ph.o8ph.orha;, tisssn acids and neutralizing amines in the same way and. All these can be used successfully according to the invention,

it was found that the preferred li-alkyi according to the invention ■ Phosphorus acids and their mixture «an acid value of about 220 to about 2 ^ 0 aiTfweieen »SoXche products zeJgeii. in Liquid Koh, -anwassersii open an excellent Uirkeami: eit against Vex-seliau ^ zung.

The processes of contamination of the heat exchangers must be taken into account in connection with the goods being loaded = in the Deetillations'beri-ieh τοη about 93 ° ~ 205 ° Z (200 ° - 400 ° F} can be a number of connections exist, which originate from the crude oil part! ati, en _?

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BATH

from cracked material to a simply distilled clay would be naphthium and bring about the oxidation of these caphthae in storage other hydrocarbon and non-hydrocarbon compounds. When considering the pollution processes The verbicizations are made individually according to the XXasa.ifi "-zierung entered *

Paraffin compounds can be straight or branched chain hydrocarbons. In general, they are verhältnisaässig at elevated temperatures against oxidation resistance "capable Fa was üerishtet that oxidized products of paraffin with oxygen in the vapor phase at 288.85 ° to 398.85 ° 0 (570 ° to? 50 ° F) were prepared * z to respond, B, n-Heptea with oxygen at 327 '7? ° C (590 ° F) to ÄthyUn and an I-'eroacyd to bildea. Acids, aldehydes, coaol, and esters are produced in the oxidation of paraffins by the formation of hydroperoxides and dihydropsroxides to form » Has it been found that simply distilled naphthas, which contain immeasurable olefins, hydrogenated hydrogen, mersaptans or dissolved oxygen _? No more traces of deposits form the heat exchangers if the temperature of the main oil maeae is not around 590.85 °

909884/1593 BATH

(750 ° P), at this temperature or a higher temperature, thermal cracking of the paraffin occurs, whereby products arise that can react in such a way that they form polymeric precipitates. As explained in more detail below metallic catalysts can take part in the reaction »

In the gasoline fraction of Hohölea Mono were - and bicyclo "paraffin found" The Monccyeloparaffine beefeehen mostly of Oycloheptan and -hexaxien with extremely small amounts of cycloheptanes The Bieyeloparaffine can from methylene "(2.2.2) -bicycloh9ptaai _i bis-bicyclo ° (3 * 3.Q) ~ octane, tetralin and eecalin consist of · Little is known of the thermal stability of the first two compounds, but their decomposition is probably similar to that of normal paraffins. Tetralin and decal in are subject to dehydration at elevated temperatures. When benzene is the end product, a more thermally stable compound is formed, with the remainder being unsaturated compounds "

Plants at refining the deeper la extend the gross mass produce zn more Bezin, do not let amazing that the heavier thermal and catalytic cracking products continuously to below 25 f "of the feed for the Gutee

909884/1593
ORIGINAL BATHROOM:

■! 545335

Identify Hydroentaehwefler and Reformers. The primarily useful product of the cracking process is a naphtha, which has a high olefin content plus sulfur, nitrogen and acid-off compounds. Boron conjugated olefin content can be up to 5 % . It was found that in many cases these conjugated olefins form the evaporation residue in coke distillates »

It is known that olefins are capable of intermediate reactions that form polymeric compounds, using metal catalysts they can also be mixed with oxygen, oxygen «organo» sulfur compounds and oxygen-organo-nitrogen »compounds react ·

Pte Oxygen-Qlefin reaction in the presence! P * tall! mtaly = satoren has variously described: “The primary reaction product is a peroxide. In an oxidation state of plus 2, the metal is capable of removing hydrogen from the olefin, forming a free radical. This free radical reacts with an oxygen molecule to form a peroxide. The peroxydfreien radicals may form by rearrangement, loss of water, a variety of aldehydes, ketones and acids and esters _β Some of these are in turn f änig, hiokungsgut with other components in Bes & su

909884/1593
BATH ORIGINAL

react and form polymeric compounds Reactions will be discussed in more detail below «

Laboratory tests have shown that naphthas that Contain cracked products, or the cracked products themselves, cause considerably more pollution and cause larger deposits on pipe systems than simple distillation products Naphthabeeouchungsgut oxygen is present. This effect of dissolved oxygen is shown in laboratory tests used by pollution phenomena to increase the amount of pollution and thus the duration of each attempt abbreviate. This is done by prior and ongoing saturation of the load with air «

The sulfur content of simply distilled naphthas can range from 0.01 to 0.1? % In the crack naphthas it can be up to 0.5 % . The sulfur compounds here are thiols (CMercaptans), heterocyclic sulfides and polysulfides, and thioethers.

It is known that mercaptans are capable of intermediate reactions to form olefins and hydrogen sulfide · Se occurs Decomposition of the mercaptan into a free radical that is caused by

90988A / 1593

intramolecular cleavage of olefins and hydrogen sulfide » gives ο The reactions at 398.85 ° 0 (750 ° F) formed quite a lot of olefin and hydrogen sulfide ο At lower temperatures this reaction was not noticeable »

Sulfur compounds can also react with the olefins and form polymeric compounds = For example, the reaction of olefins with mercaptans *; in the presence of Oxygen has been described with the formation of a substituted 2-hydroxyethyl sulfoxide.

Numerous nitrogen compounds have been found in crude oil ο Simply distilled naphthas «obtained from high nitrogen crude oils contain some of the low molecular weight cyclic or heterocyclic nitrogen compounds. Another source of nitrogen compounds in the Refor » mation of the load is cracked naphtha * crack » Naphthas with a high nitrogen content are usually strongly colored and have a great tendency to contamination, that is, the formation of deposits also in laboratory tests.

The naphtha oils coming from the refinery usually contain traces of dissolved or suspended metal salts,

909884/1593

• Χ)

which originate primarily from corrosion processes =, verifications show that not only copper, but you, nickel and chromium, the formation of deposits; can increase _n

So far; only possible chemical reactions in the formation of exchanger deposits were taken into account, these Reactions are most likely through! Peak, pressure, Flow rate of the mass, residence tent and the physical conditions of the "reactor", in this case the Auetauecherrohrea, influenced.

Ke has been found to have increased temperature and dwell time generally increases the pollution rate. The flow rates depend on the pressure and the volatility of the load. If a • iBeaehickegut is evaporated, the heat flow to achieve a special

The fishing temperature is higher than when there is no evaporation. The surface temperature of the Würmeauetauscherrohrrohr is higher, so that an increased cracking or coking is the result. However, the increasing speed of the gaseous naphtha tends to "sweep" the surface,

) removing some of the coke, giving the appearance of less pollution. In this area, the type of coke made cannot be seen. ^v "t this stripping or"^Fegon!; lead and the Geackwiadig ~ cold will only have a small effect ~.

909884/1593 BATH ORIGINAL

Course ausaaroengefasst it is found that the reakticna £ uhi6 © * i Olefins in terms of <* taingr. £ Ut Ymvery capable through traces of 2feta2! catalysts free radicals zv. form., which then react with oxygen uad toroid «». l> 3? dca "csmu'c-Λ The peroxides react with themselves.- apXbat, with Sei rofoiunrl'oder Nitrogen compounds tniä bilde », pol

• on the heiseön HetaXlflächen of Auateus (? H9rro.bx '( "e uiwi to the BeÄ ^ ickungsgut existing". Koi * roaioi> .sp? 9dukteu <iu ~ kiebenc AcsclLliesseun occur at the AuetauscheroberfltUilie reactions to _r di.'" the Abdampirüsketandeniederac ^ ag in coke etched with * corrosion product unchanged, "

Oils invention removed see from the theory of dispersing agents to erosion of the verse-bmuts'uag tsh helssen V / äraeant-iauecherfläebeno It was found ^ that the verse-bmuts'uag. hot surfaces of heat exchangers, ϊθχ>. are r4un · = _F gene Haphtliais and crude oils in hydrocarbon komiaen IAIT erfindungsgemlissen additives ^ considerably combated ^better-: \ md the like, 'which in working operation, in' he lower Berülmmg with liquids or vapors το && Alkaaen, lower Alkenes ,, aromatic verb can ale with commercially available Dlspe-rgiermitteine Xn de: ι-reaching cases considerably geringere- Hengen an a & tivor.sehmut außgsmi ttels, daa in a to-m £ f lniereütd'an Pc ^ releuia

90.988 ^ / 1593 ORIGlMAt BATHROOM

greed or resolved _t as much as were necessary, except. It is assumed that the eriAdunsßseaäcfi bewonfUtai ¹ , ehmutzuiifsaraittöX less by a binporeicBn <or by preventing polyiuorisati.oiiOD r in

by adsorption or reaction. the £ smiles work ο

According to the invention additives are added to the before? Contact thereof with the HE ie sea Wäraeaua = tauaehoroberfläche eye sets and dispersed therein _B woboi the formation of Vorsahnutzung reduced w'ird "The dom B" ßöhic] iunsßgut komaonde in touch surface of the Wärae ifiit: in a Durchf3, UBS "Wär £ iQauetaueclie .r

pj "e das Beschieku ^ gsgui? χυαά is about 9 ^ * 35 ° ° ^ Ο9ί5 ° Q ⁽ '2ΟΟ ° - SOOC ⁰ F),

J>: lc Prfindim ^ fiffeiiass VGrifeadetexi ffongQü dec additive x-eibiiön voa ^ ¹ X- ^ M bis au iQCD - aOQO -Ϊ / Μ, in some cases b? ss% 50C "C / Ϊ / Μ« ßiö optimal use-bejpe treatment limit henfjt of the type dee B ^ Bchiekungoguteat the arboiteweise, which is subject to _f ? £ rd f and the temperature _t to that of the toeson-

Ko3aJbC ^: v.'aB3 £ 5r.'3 ^ off erv; ärist is, from "AL ', s alXgemei applies that one- I * gi \ ge ν" ι awieohozL i ΐ / Η 5ai.a to 1000 for the time being 5 --- - ³ ^ - Of / 'M ₉ yorwendefe becomes ₀

90988A / 15 9 3

BATH ORIGINAL

One of the most interesting cardboard boxes of the invention is that the additive stays with the liquid phase during the various refinement stages, so that, for example, a gas oil is subjected to a cafealytic process, the additive nl ^ hfc in an aerk ~ «lent Auemass in that the end product; over _r aüEÄora remains with the residue and the indistinguishable umgewandeitoa components are liquid JBurüek or soratört catalytically,

? I .io additives könnsn de: i 3eachle cungegi \ t be zugegobon to irgeadeiueu funct the 'process u d sYou we; FSelect aitgefUbI ¹ ^ ₉ to au the Eaffinationnvorgang * at doei daa product Lu is converted to another chemical Yerbindung or new strain _c

Thus, _there's where a Hohgufe to remove IEIC-hteser functions zn heat exchanger thermal JDeetil led lationßanlage, the additive is added immediately before the heat exchanger "Daboi protects both the Auatauacherobarflächen and other of distilling ^ - or raktionieronlase? _β

If ui spoken of Schuts the vei'si-hisdenea equipment is straighter one that ρ daa rJescaicki-ingsgut the ofeosflachen Who-aöäusliBU as Metal ', plead "" pulls in yeraehmutst, ao -, laos

909 ^ 84/15 BATHROOM OGA

no deposits are deposited or _c deposits are deposited o As a result, the procedure can be described as preventive or corrective, »In some cases the additives remove already existing soiling aungj meiscans, however, they prevent the pollution rather than removing existing deposits ₅

The advantages of the inventive method and the Addi- = The examples below will make them clearer

The ver to evaluate the antifouling property "sohiedener connections Laboratoriumaanlage used consisted of a boiler for the chamber load, a stick" cloth printing system, a valve and Rotadurchflussmessor to control and He ^ eXung of AbbXasens of nitrogen from the Dep & llkessoÄ "valves to control the Beschickungsgut- £ lusaes from the fuel tank to the warming zone and waste boiler ₉ and from ulcer Väraozone _? of an annular heat exchanger, flows through which the charge material and which is composed heated to temperatures triebsanlagdn at Be "usual aixd- The flow of Beachickungaicessel to the Abfallkeesel through the heat exchanger takes place in that the pressure in the Abfallkesael is kept lower, -. in Beechickungskeeeel »

909884/1593 BATHROOM not ok

Paa charging material, which on the bottoms of Austauscherau "position passes, has room temperature and the desired bridge, if that well aufeteigt ira exchanger is θ η to temperatures of 37.78 ° C (IGO ⁰ P) to about 537.75 ° G (ICCO ⁰ F) heated to au-1093 * 30 ° C (20X> ° F). During this rapid feiaperaturäademing the good and forms particles _t tend to be larger at the

£ he determination ΰ.-ve Ve ^ nshatutzmisoraten davch waste dtx ·

coef ^ iaieaten is in unity en _t vio Yar aui'triti, nelir aehwierig. It Wirde therefore benchloaein empirisshes aalbquantitatives Rechenaystem lor the Wärni © ff.ustav.iiclie ^: - i3bye ku aehafTeß ₉ bai dsm a Meeaiirg dee of iJeder Art de? Deposition covered »Berei.ehea uu / i eiJie visual SeJiätsvng Äer severity of a ^ e & ea deposition duroh-

$ io in the Hfeme.mfitsriseharaniagi; »» geVildetsn hang, from, the Jk:?% ueo Böß '». hiekussSBgiitefl and ab _o here isiiid aowohX Oberf? -Eeböat © ap © ratur a3, a also dio« es? Flilsei ^ ait weeont ^ iehe Feüctcraa, Piß

der AtAarj ^ rnangen Jccmii yöe. ei & er geIfc "brauE, ea _{ g Kaes ©« <sxi? oij '^ ra he.T, ioa I-aei: cm cool Hilde mn

90988A / 1593 BAD QRiGJNAt.

56 -

ree up to heavy coke on the hot end o The kind the deposition on every recognizable area of the pipes de alt dom eye according to the following system propositionv *

?: '? Mg. or

^ t - (?; -> (? »er. ^ l.ae · απ« ί> ·; .σ2

fep; €

ffiäsßi iieaes ^ v'iäir, o3-.3.ar _f - föcliä ^ awüis wusde the each area, au dera Heb * ¹ pertaining and with üqt? iaittier3.u Xaäcge e ^ Äes & eaexL area ilene numbers wurdon addiex-t to the (Jesamt-

This Yergeh ^ iL is & i «? 3h deia the following example explains! Aj't of the hf

"ά

© r oittio ™ brighter aehworer rer La «?. k coca 3 6th 2 6th i -Ji 4 C4) ² χ 6 16 * 18 96

909884/1593
BAD ORiGiNAL

This Berechnungssyatein presses the quality and quantity dös by thermal decomposition of Beachiclcungsgutea gebii data Kokiaes and r; Xeichzeitig it comprises the dureh Abdampfrücfcatände deposits formed already vox'handon In seliielcungsgut or check during DSSB E form ₀

and Haci.thagisKiscae v / urden by 5.0 ^ u

®vb "Mess was arJfordoi ^ licii, because just tended to" - dao tax and HegeX ^ ent ^ i to veretopfea _c

Bi) sc> \ icIcungi3 £ 5Ut was not ventilated ₉ alao not; air "and it was ensured that daao Jceice XAift-Äiaphtha-

Thereby the formation of AMarapirnekstaisd in the Trorn uel was reduced to an iüßimua and that in the laboratory uatersmch ^ on iiaphthas corresponded to "

diea2 Wfjisö waitgehoad which _t die
and processed _a

Mi »versehledonen SsuQÜLartea are in & ea fol goadea.Sabellen aussameßgeatellfe .. The 'XOstbodittgungen eat spoke to those who occurred at tfäxueaustauschurna ₃ who were arranged in a work cycle immediately in front of the oven

BATH ORIGINAL

ol examined in a facility at 47'.6 atm;

SO-D al per hour 332.20 ° C (650 ° W ).

Additive »
example Additive"
«Ease T / M Pipe
worth ^ 58 VIII 100 14th VIII 50 19th VII 300 20th

the ver «

76 6? 52

labella IV

Kerroain tested in a facility at 47.6 ata (7C-0 pel);

800 ml t> ro Stds 595 "%" ° CC 740 ° Wi

Additive
Example additive
share I / M Hohrbe = Lowering the
Dirty itemsB & e % VIII 50 27 50 VIII 100 8th 85 VIII 200 6th 89 VIII 400 6th 89 VIII 1000 4th 95 - 5 *

909884/1593 ORIGINAL BATHROOM

! • bark V _t ent at 4-7.6 atm (700 t> il): Xheralieh fjceta * acked SaOhth UiO stds 393.30 ° C (740 ° P) Beaohiekun RBWQTlXB - 800 ¹¹ Al Hohrbe-
Wertunic Lowering the ver ~ Additive
AtBDiel Zueatz-
aentce T / n 58 - - - 13th 78 VIII 500 15th 74 IX 50 18th 69 II 50 23 60 III 50

It goes without saying that a number of codifications and Changes are possible that are easily recognizable to the iuchan and do not affect the concept of the invention.

909884/1593

BATH ORIGINAL

Claims (1)

o / Additive to prevent contamination by organic and inorganic deposits from a hydrocarbon charge which comes into direct contact with a heat exchanger surface, which has surface temperatures of about 37 ° to about 1094 ° 0, characterized by a content of an N-alkylamido phosphoric acid from the group of the following compounds: (A) (B) (G) HO I. OH NR ₁ Rp [■ P - NR ₁ R ₂ OH R ₅ R ₄ R ₅ HH II O - P - NR "R 1 * 2 90988W 1593 ORIGIMAL BATHROOM -IH- R ₆ O - P - NR ^ Rp OH (E) R ₆ O - ΪΙ P -I OR * (G) R ₆ O -1 • ο NR ₁ R ₂ J 0x0 NR ₁ R ₂ 0 HNR 3H ₄ R ₅ -J * 2ο additive after. Claim 1, characterized in that R ₁ and R _{2 are} the remainder OH _x - C- OH CH _x CH ₂ -C - R ₆ the rest CH 1 CH _x (CH ₂ ) ^ CH mean· 98 84 / 15.9 3. Method for preventing spillage by organic and inorganic deposits from a hydrocarbon charge which is with; Heat exchanger surfaces, which have a temperature of about 37 ° to about 109 ° O, comes into contact, dadusoh marked that the Beaohickungagut an additive according to claim 1 or 2 is suggested. 4. The method according to claim J, characterized in that the hydrocarbon is a su-refining petroleum and from naphthas, gas oils, crude oils, raw gases and / or Consists of petroleum gases, 5 · Method according to claim 3 and 4 », characterized in that that a petroleum waste, which is refined su petroohemisonen materials, is used. 6. The method according to one or more of claims 3 to 5 t characterized in that the H-alkylaminophosphoric acid the hydrocarbon in an amount of about 1 - 3000 T / M be absorbed to the weight of the Kohlenwaaseretoffbeediicioangagutes is added. 909884/1593