DE2950482A1 - METHOD FOR IMPROVING THE PROPERTIES OF COAL LIQUID PRODUCTS AND SOIL PRODUCTS - Google Patents

Description

ΙΙΟΙΛΚΜΛ'Λ'Ν · Ii I Ti, J ^ Λ .VATfTNTOR ι · ΛΊ ι; χ'J ¹ A ν \ ww.rn

DR. ING. E. HOFFMANN (1MC-1V76) · DI Pt.-I MG. W. Γ Π I I. · D R. RI f. N Al. K. Ii OF FMAN N · DI Pl .. IN G. V /. IF Il N

DH'l.-ING. K. ro CH St C · DR. RFR. MAT. D. HANStN ARABElLASTRAiSfMST ¹ RNHAUS) · D-BOOOMIlIJCHFNiI · IClL Γ O TJ (OtV) 9) 10 67. TE LF. X 05-2961? (ΓΛ1 Il F.)

32 829 o / v / a

EXXON R]] SEARCH AND ENGINEERING COMPANY, FLORIIAM PARK, N.J. / UNITED STATES

Process for improving properties von Kohjoverf 1 liquid products and floor products

The invention relates to an improvement in the heavy carbon fractions and in particular an improvement in the solubility of the heavy coal fractions in common solvents and petrochemicals.

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In processes for liquefying coal and similar carbon-containing solids, the material added is generally brought into contact with a hydrocarbon solvent and molecular oxygen at elevated pressure and temperature. As a result, the complex high molecular weight raw materials are broken down into low molecular weight hydrocarbon liquids and gases. These are recovered from the liquefaction effluent, leaving behind the heavy liquefaction bottoms, which normally boil above about 537 ° C (1,000 ° F) and generally contain suspended solids. The bottoms of liquefaction can make 50 or more wt.% Of total liquefaction products.

The ilaupLanwondung of liquefied coal, especially of high r. i odondon Kohlef lü ^ si ykei th, ordered in Treibstof "blends of both coal and Pot lüssigkoiten roleumf Unfortunately Kohl.of 1 U3 J gkc older how such ^{one, egg;!.?..} ο you drive through Ilydrierungsver is not compatible with the Pctroleuinflusr.igkeLt.cn, so that the addition of small amounts of the coal liquids to the Petroleu'iiflüysiyen leads to precipitation.

Without dv'iss a certain theory can be established here should, it can be assumed that the aforementioned precipitation occurs because the coal liquids are more polar than the Petroleum fluids due to the presence of phenolic and carboxylic functionalities. These polar functionalities cause an intermolecular one Association between adjacent coal liquid molecules and tend to carry the carbon liquid molecules through

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OWGiNAL INSPECTED

a network of hydrogen bonds ... to keep one another. Petroleum fluids that these polar functional Groups don't have the ability to participate in this intermolecular Association does not participate. As a result occurs a separation and the petroleum and coal liquids separate with formation of distinct layers.

A variety of different methods of improving coal liquefaction soil products have been proposed. It is known, for example, that the bottom products can be pyrolyzed, i.e. gases, other hydrocarbon liquids and coke are obtained, whereupon the coke is subjected to steam gasification with the formation of hydrogen and carbon monoxide for use as fuel (see US Pat 4,060,478). An andoi.v.-; Processes for improving liquor base products are described in U.S. Patent 4,089,772. In this process, an acid cat a 1 ya i er t "o CA] kyllerinio or C-Acyli eruiuj of the iodine product to. Ans of the coal discharge before recycling of the doden fraction into the liquefaction reaction. onszone instead.

These numerous processes result in better utilization of coal liquefaction bottoms. in the However, the following Kohlover approval has been given before driving Phenols from the coal with the formation of water ycEpalten.ini Liquefaction process using hydrogen there is therefore a very high consumption of hydrogen.

With the solvent extraction of coal one remains

030026/0808 ORIGINAL INSPECTED

high molecular weight insoluble fraction of coal, which mine calls insoluble coal soils, back. Similar to the soil products from coal liquefaction One can also get this heavy fraction through a number of grafting processes subject to achieve an improved yield of liquid.

According to the invention, functionalities with weakly acidic protons in coal liquids and heavy coal fractions or bottoms are subjected to alkylation or acylation (which is often referred to below as oxygen or O-alkylation or oxygen or O-acylation). Weakly acidic protons include phenolic, carboxylic, and mercaptan functionalities. The O-alkylation or O-acylation is most easily carried out using a phase change reagent and an alkylating or acylating agent. The phase change reagent that can be circulated is, for example, a quaternary ammonium or phosphonium base (R.QOR "), where each R is an identical or different group selected from C ..- to C _Of) -alkyl and Cg- bis is about C ₂₀ ~ aryl; Q is nitrogen or phosphorus and R "is hydrogen, C - to about C - ^ - alkyl, aryl, alkylnryl, arylalkyl or acetyl. The alkylating and acylating agents are characterized by the formula R ¹ X, where R ^{1 is} a C _{1 -C 20} alkyl or acyl group and X is the leaving group selected from a halide, sulfate, bisulfate, acetate or stearate and wherein X is attached to a primary or secondary carbon atom.

O-alkylated and O-acylated carbon liquids and heavy

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Coal fractions exhibit in common organic solvents increased solubility and are associated with petroleum fluids better tolerated than those that were not treated in this way.

The process according to the invention can be used advantageously with all Soil products of the Koh] liquidation, regardless of their Origin, made v / earth.

Coal liquids and heavy coal fractions (soil products) are materials that are used in a wide variety of processes from coal, including hydrogenation processes or a donor-solution reaction which one sticks out Koblef fluids. Soil products the liquefaction of coal, which is merely a by-product des Vei f.i ü.ss j gungr. seduce pose, pose a undesirably large fraction of the total liquefaction productc A typical liquefaction process under Using a hydrogen donor solvent in U.S. Patent 3,617,513.

Doden products that are produced when coal is dissolved, are such residues that one can get from the coal at a Much has been obtained from solvent extraction processes. A typical example of this type is described in U.S. Patent 3,607,716 relating to supercritical gas extraction.

The alkylation or acylation procedure described herein can be used advantageously with all heavy coal fractions, regardless of their origin. This one used terms "coal soils" and "sweat fractions" have the same meaning and relate to

030026/0808 ORIGINAL INSPECTED

Coal residues that are used in coal trading ancestors, such as Coal liquefaction, coal solubilization and the like, attack. In certain gasification processes falls as a by-product Tar on and this is also regarded as a coal residue, which according to the inventive method can be treated.

In the process according to the invention, functionalities chemically changed with weakly acidic protons in the treated material. For example, acidic proton-containing groups, such as phenolic groups or carboxyl groups, which represent very polar functional groups, converted into relatively non-polar ethers or esters. The chemical conversion can be represented as follows:

Ar - OH + R ¹ X -> Ar - OR ¹

Ar - COOII + R ¹ X> Ar - COOR ¹

wherein R ^{1 is} a C ₁ to about C _2o alkyl or acyl group.

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Uic O-alkylation or O-acylation of solid carbons by reagents that are considered liquid. Solution present becomes significant through the use of a phase change agent influenced. Such a reagent has both a liophilic and a hydrophilic part and is able to a basic species, -OR ", from an aqueous phase to both solid and liquid organic Phase, where R "is either hydrogen or a carbon-containing functionality. The phase over Access agent can be formed catalytically, in which case the process is as phase transition catalysis and is a known reaction (see, for example, Journal of the American Chemical Society, Vol. 99, pp. 3903-3909, 1977). Alternatively, the phase transition agent can also be used in a separate stage can be generated and then used later in the alkylation or /cy.lierangsreaktion. If you turn this If the latter reaction occurs, the active form of the reagent can be regenerated in a subsequent stage. In In both cases the total chemical transformation on the solid coal is the same. A general scheme this conversion is shown below:

-> R.QX + M: 0R "^:;R.QOR" + M: X

Carbon-H + R ₄ QOR ¹¹ > KOhIe-QR ₄ + R ¹¹ OH

KOhIe-QR ₄ + R ¹ X> Coal-R ¹ + R ₄ QX

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The phase change material is preferably a quaternary formula of formula R ₄ QOR ^11, wherein each R is same or different groups, avisgewählt from the group consisting of C.- -C _2f -, preferably C ₁ - to C, - alkyl, and Represents Cg to about C ₂₀ , preferably C _β to about C ₁₂ aryl groups; Q is nitrogen or phosphorus, preferably nitrogen, and R "is selected from hydrogen, Cj- about C ₁₀ -, preferably C ₁ - to Cg-alkyl, aryl, alkyl aryl, arylalkyl and acetyl groups, preferably a C ₁ The phase change agent can be formed by reacting the corresponding quaternary salt R.QX with a metal base MOR ", in which X is a halide, sulfate, bisulfate, acetate or stearate. X is preferably a halide selected from chlorine, bromine and iodine, and in particular chlorine. M is selected from the group consisting of alkali metals and is preferably sodium or potassium. As shown above, the quaternary base is reacted with the acidic groups in the carbon, which in turn ^{react with at least one alkylating or acylating agent of the formula R 1} X, in which R ^{1 is} C ₁ to about C _9n alkyl or acyl groups and X has the meaning given above and X is bonded to a primary or secondary carbon atom. Preferably, R 'is an inert hydrocarbon, ie, a hydrocarbon group containing only hydrogen and carbon, although hydrocarbon groups with other functionalities may also be suitable for the present application but are less desirable. It remains to be seen that the acidic proton H (hydrogen atom) is generally localized to phonolic groups in higher-quality coals and on in inferior coals

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Caj-hoxyjcj'upjjcn. The acidic proton can also be in a lesser one Aunno of sulfur, nitrogen and the like be bound.

Phüijonübercjanysi'.u ttel, like an equatorial ammonium base (R ₁ OuR ") are in the O-alkylation and O-acylation of carbon sel: r v.'irknam. These O-alkylation and O-acylation jureaki-ions are successful because the -OR "part of the molecule is soluble in an organic medium. If this base is present in such a medium, it is not oxidized in this way by water or other strongly polar molecules. In the unsolvated state it can then react as a proton transfer reagent. A) j ("'i: y \>. Iv. ). Is an inferring affection:

(HoIiIe) -OII H OR "> (charcoal) -0 + R ¹¹ OH

Di <- ■; ..> ■ unsolv.'iti si crte liasc (also alr>"nakedhydroxide" lv I '.. ··.:. V; t, v.'or-in] V ^: Kanrerstof f means ) kr.nn a variety of (Vyonionen Halmen. Although the counterion can be one of the aforementioned quaternary / uiunoniuiu- or Phosphcniumspe-ζ ic .: s, others are suitable in the practice of the invention, v,. D. " Crown ethers ", complexes of salts containing the OR" anion, and inclusion compound complexes with a salt containing the OR "anion. Salts of the ΓοπγιοΙ MOR", in which M has the above meaning, produce a reactivity after complex formation with crown ethers is similar to that found in R.Q0R "-visions.

According to one embodiment of the method according to the invention becomes an x.v.-phase solid-liquid or liquid-liquid system from the coal soil products or the

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ORIGINAL INSPECTED

Carbon liquid is formed in liquid suspension. When the coal bottoms are heated, they can be crushed into fine particles such that they are particles less than about 6 mm (1/4 inch), preferably less than about 2.0 mm (8 mesh NBS screen size) and most particularly preferably contain about 0.17 mm (80 mo.sii). The smaller the particle size, the larger the surface and the faster the alkylation or acylation takes place. It is therefore desirable to expose as much of the coal surface as possible without losing the coal bottoms as dust or fine particles, or without compromising the economics of the comminution. Therefore, plate sizes greater than about 0.0-1 mm (325 mesh) are preferred. In FaIJe the Kohleflüssigkeiton can also ejn Prcipbacen-ftystem from the Kohlff 1 ü ¹ ·; .irjj-e.it nud an aqueous Pha.se, znsaninion with a JVtroleumf lüi ":: i ■ jkeit anv / cndcri.

It is not absolutely necessary, but you are luuin Add a solvent if necessary. The solvent can be used to locate the al kyliert'n odor acyl j to dissolve or represent carbon-containing products. To dissolve alkylating or acylating agents (especially if this agent is a solid and proportionate is insoluble in water). The solvent can also serve to effect better mixing. Many of the usual organic solvents can be used in usual amounts depending on the desired result will.

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The phase transfer agent used must be dissolved or suspended in both phases so that there is intimate contact with both the organic and the aqueous phase. In the course of the implementation it will then turn out to be; Divide the phases into both phases. Quaternary bases, which are one of the compounds which are suitable as phase change agents in the practice of the invention, have the formula R, QQR ", where R is an alkyl group having at least one carbon atom and preferably 1 to 20 carbon atoms and most preferably 1 to 6 carbon atoms!, or an aryl group G is up to 12 carbon atoms ,, a Verbindungsphnne, which is in the present *. a low number of carbon atoms are preferred because these compounds are more water soluble and aim the alkyl .i locate odor aoylicrten Koh Onboclonal products can be removed by simply washing them out with water.! Vi /: R groups can be identical or different. Examples for R groups are methyl, butyl, phenyl and coxadccyl.

Examples of quaternary, inventively applicable Arimonium bases are:

* Continuation is used as a phase transition

where τ / lon

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(1) Trabutylainmonium hydroxide, (C.Ug) .KOH (?.) Bonzyj hexadecyldimethylamruonium hydroxide,

(C ₆ II ₅ CIi ₂ )) C ₁₆ H ₃₃ ) (CII ₃ J ₂ NOIl (3) Tetrabiitylphosphonimnhydroxid, ( ^C / ^H g)

(4) ADOGLN 4G4, (Cg-C ^) ₄ NOH, (ADOGEN is a trademark of Aid), i ChcnJ cal Company, Metuchen, NJ).

The metal base that is used to convert the quaternary salt into a corresponding bane is an alkali or alkali metal base, such as KaOH, KOH, Ca (OH) ₂ or NaOCII ₃ . The use of an alkoxide enables, for example, the use of the corresponding alcohol instead of water, wn :; May be of advantage in the treatment of KoIjIebodonproduktecn under such conditions, in which water is undesirable.

Bc-i Cf. : /iur.v;a!il dvr. A3.kyli erungs- oder 7vcylieruny: jJüil te] :: - MÜL »:". C ^j n two considerations are taken into account. First, it is desirable to attach longer chains to the carbon liquids or - to add soil products, through which these .products become more petroleum-like and therefore more soluble in organic solvents and more compatible with petroleum liquids. / On the other hand, the shorter chains make the alkylated or ecyliortei: colile liquids or soil products more volatile. On the other hand, short-chain materials are less expensive and yet increase solubility.

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ORIGINAL INSPECTED

-1G-

In the O-alkylation, the carbon atom to which the leaving group is bound to be either a primary or secondary carbon atom. Primary carbon halides react faster than the corresponding secondary halides in a phase transition or phase transition catalyzed reactions in the case of carbonaceous materials and are therefore preferred. Although the carbon-containing functional groups too may have other constituents, such as heteroatoms, aryl groups and the like, the bond takes place carbon-containing functional group on the phenolic or carboxylic oxygen

either by an sp -hybridized carbon atom (alkylation) or an sp -hybridized carbon atom

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(Acylieruny) · A mixture of alkylating agents or Acylating agents or a mixture of both can preferably be used. Such mixtures are used in Coal processing plants in other process stages frequently formed and therefore represent a source of alkylation and / or acylating agents. Examples for alkylating or acylating agents suitable according to the invention are ethyl iodide, isopropyl chloride, dimethyl sulfate, benzyl bromide and acetyl chloride.

Although you can according to the invention alkylation and / or Use acylating agents, however, alkylating agents are used preferred for the following reasons. First, alkylating agents are easily made from the corresponding hydrocarbon Leaders available. For example, you can easily replace alkyl halides with free radicals Halogenation of alkanes, a well-known procedure, produce. If a system with more than one alkylating or acylating agent is used, then is the hydrocarbon precursor is preferably a product stream from certain cuts from the coal and pelroleum processing. This stream can have small amounts of components with different saturation, the are also suitable for the reaction with phenolic and carboxylic groups, as long as X (with the previously given meaning) to an alkyl or to a saturated hydrocarbon atom in the resulting Alkylating or acylating agent is bound. Second, acylating agents are prone to hydrolysis. Since water is always present in coal and also in the case of the invention Method employed may involve some loss of the acylating agent through hydrolysis occur. In contrast, alkylating agents do not show this

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Sensitivity to hydrolysis.

If the O-alkylation or O-acylation is carried out by a catalytic Procedure carried out, the quaternary salt, the metal base and the alkylating agent:> the acylating agent mixed directly with the coal liquid or an aqueous slurry of the coal bottoms. The quaternary salt catalyst can be used in small amounts, typically from about 0.05 to 10% by weight, based on the amount of coal bottoms used, but larger amounts can be used will. The metal base and the alkylation or acylation.?- agents must be in at least stoichiometric amounts, based on the number of acidic sites (phenolic, carboxylic) in the coal liquids or bottoms may be present, but they are preferably used in excess to complete the reaction. It is advantageous to use a twofold excess the metal base and the alkylating or acylating agent on, although a larger excess can be used. After implementation, you can use the Excess base and the quaternary salt catalyst from the coal liquid or bottom product by simply Wash out water and recycle excess Metallbaso can also be washed out by water and then reused, excess Alkylating or acylating agents can be easily obtained from the treated carbon material by fractional distillation or removed by solvent extraction with pentane or another suitable solvent and then be reused.

* wash with

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To get all acidic protons in a carbon liquid or typically used in a catalytic process to convert a -floor product, less than 2 days are generally required for a 100% conversion, if you only have a small excess of alkylating or acylating agents and coal bottoms of a size less than 0.17 mm or carbon liquids at atmospheric pressure and temperature. A larger excess of alkylating or acylating agent reduces the response time considerably.

Faster alkylation or acylation can be accomplished in a number of ways. One of the methods is to add the phase change reagent (R.Q0R ^{! :)} directly to the carbon liquid or carbonic products instead of forming the reagent in situ during the reaction, in which the carbon fractions are alkylated or acylated. If one works in this way, a complete conversion of all phenolic and carboxylic groups can be achieved in a few minutes. The amount of quaternary base added ranges from about stoichiometric proportions to about 10 times the total number of acidic sites in the coal liquid and / or bottoms which can be alkylated or acylated. As stated above, the quaternary salt formed can be recovered in the alkylation or acylation step and reacted in the circuit with fresh metal base to form the quaternary base. If this two-step process is used, there is no contact between the metal base and the carbon bottom products and the reaction is essentially complete in about 1 hour.

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Another embodiment is a mixture from the coal liquids and the petroleum liquidson and the alkylating or acylating agent with an aqueous solution containing the phase change agent, treated. The alkylation or acylation can be catalytic or non-catalytic in the manner described above Procedure.

The temperature at which the reaction is carried out can range from ambient temperature to the boiling point of the materials used. Increasing the temperature naturally increases the rate of the reaction .

Dar. Roiik'tion mixture can be stirred in any way or moved to the interface between the surface to increase the phases and because aqueous, organic liquid and / or solid coal bottoms phases are present ε i η d.

The reaction takes place under ambient pressure, with an iichv.'ach increased pressure (about 2 to 20 atmospheres) and Heating can be used to increase the rate of reaction.

After the reagents and solvent are removed from the alkyl or acylated coal liquids or bottoms have been removed, one can determine by infrared analysis that or whether all hydroxyl groups alkylated or acylated. If the admitted If the alkyl or acyl group is IR-active, a corresponding infrared frequency is observed. If desired, can

030026/0808

ORIGINAL INSPECTED

andore known analytical methods are used. the Final analysis on the percentage of C, H. N. S and O is so changed that never with the expected change based on the added alkyl or aryl substituent matches. For example, increasing the H / C ratio in O-methylated carbon bottom products from Illinois No. 6 Coal states that adds 3.5 methyl groups per 100 carbon atoms to coal bottoms have been. The II / C ratio in untreated coal soil products from Illinois No. 6 coal is 0.754, while the H / C ratio after methylation according to the invention Method is 0.790. The therinograviirietriscne Analysis of the methylated coal bottoms shows a marked increase in volatile organic constituents compared to the untreated coal soil products at (40 "; opposite 3 8 S).

If coal liquids are treated, the increase in H / V prevention! r. '. er, von O-methylated coal liquids from Illinois No. 6 coal, that 3.5 methyl grujrji-n per 100 carbon atoms were added to the coal liquid. The H / C ratio of untreated coal liquor from Illinois Nt. 6 Coal is 1.004, while the H / C ratio according to the 0-Mothylicrung according to the invention is 1.037. The treated coal liquids become more soluble in common organic solvents. For example, the solubility (20 ° C) of O-methylated coal liquids in cyclohexane increases from 11% for the untreated coal liquids to 63%.

The alkylated by the inventive method and acylated coal fluids are matched with petroleum fluids compatible, such as the increased solubility of the

030026/0808

ORIGINAL INSPECTED

alkylated and acylated carbonic liquids in petroleum liquids will be shown. Mixtures of coal liquids treated according to the invention with petroleum liquids are more stable.

The lindunqugemasc handled carbon body products can in the process from which they originate, for example the Liquefaction, gasification or solubilization, recycled will. The liquid products obtained are more compatible than those that can be obtained from untreated coal soil products receives. The solvent extractability dor Kohlebödc.n becomes considerable after O-alkylation or O-acylation elevated. As can be seen from Table 1, the solubility of Illinois No. 6 coal bottoms in usual organic solvents according to the oxygen me thy I ie ι uikj increased.

allöl Iu I

I :: SOLUBILITY (BL ¹ I 1 ATMOSPHERE) (DMMF)

Illinois Kr. 6 coal ground products

O-methylated Illinois No. 6 Coal Soil Products

toluene

Tetrahydrofuran

60 9.'S

Coal liquids obtained by solvent extraction obtained from coal soil products treated according to the invention have an improved quality and an increased quantity

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ORIGINAL INSPECTED

[compared to coal liquor obtained from untreated coal : open up.

i EXAMPLES

Each game 1

3ine from Illinois No. 6 charcoal using the Exxon donor solution method recovered coal liquid was treated as follows.

fiin 250 ml round bottom flasks were flushed with nitrogen and fitted with a mechanical stirrer. Then were charged: 5.0 grams of coal liquids (343 ° C to 566 ° C (650-1050 ° F) from an Illinois No. 6 Hydrogen Donor Solvent Liquefaction Process), 0.25 grams of tetrabutylairunonium iodide, 50 ml of toluene (pure for spectroscopic purposes, purged with nitrogen), 35 ml of a 20% strength aqueous NaOH solution (purged with nitrogen) and 11.0 g of iodomethane (added dropwise with vigorous stirring. A nitrogen atmosphere was maintained for 5 days until it was assumed The layers were separated in a separating light. The organic layer was washed 11 times with 150 cm portions of water to remove the base and the catalyst. The toluene and residual iodomethane were vacuumed at 100 cm ⁰ C deducted.

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The solubility (20 ° C) of coal liquid vacuum gas oil in cyclohexane increased after the phase transition catalyzed O-methylation process in cyclohexane as solvent from 11% to 63%.

Ks was an increase in the solubility of the O-methylated carbon liquid vacuum gas oil in a petroleum liquid made from desulphurized Aruba high viscosity heavy oil
compared to an untreated one by 1 or 2 orders of magnitude.

Examples 2 to 5

Phayeniiborqan qs]: ata glazed alkylation

The following reactions were carried out with various carbon liquids using the reagents given in the table below in the amounts given
carried out.

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Tabel

PHASE TRANSITION CATALYZED REACTIONS

O co O O

at
game Coal liquid solvent Catalytic converter (1) 10% alkali (2) R ¹ X (3) 443% 2 Vacuum gas oil Xylenes B, 3.3% NaOH, 12% C ₄ H ₉ Cl, 570% 3 Vacuum gas oil toluene B, 5% NaOH, 12% C ₂ H ₅ J, 1100% 4th Vacuum gas oil toluene τ, 5% NaOH, 20% CH ₃ J, 200% 5 Vacuum gas oil toluene T, NaOH, 12% CH ₃ J,

Definition of symbols:

(1) B is banzylhexadecyldimethylammonium chloride and T is tetrabutylammonium chloride; Percentages relate to the weight, based on the weight of the coal liquids.

(2)% by weight, based on metal base in water

(3)% by weight, based on the coal liquid

to Ln

ro

CD cn ο

Examples 6-14

Bottom products from coal liquefaction of Illinois Nr. 6 and Wyodak coal were treated using said in the following Table II reagents in the amounts indicated. In all cases the reactants were mixed for 1 to 2 days at ambient temperature.

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PHASE TRANSITION CATALYZED REACTIONS

I. at
game Soil products
Coal Liquefaction (1) Solution
middle Catal
gate (2) 20% alkali (3) R ¹ X (4) 2920 ξ I. 6th CLPP soil products
Illinois No. 6 (-80) benzene 3, 10% NaOH, 50% C ₂ H ₅ J, 3900 7th CLPP soil products
Illinois No. 6 (-80) toluene B, 10% NaOH, 50% CH ₃ J, , 158 _% i 8th CLPP soil products
Illinois No. 6 (-80)
I. toluene B, 10% NaOH, 50% Propargyl bromide 526 O.
"O co
O 9 CLPP soil products
Illinois No. 6 (-80) toluene B, 10% NaOH, 50% Allyl bromide, 460 O
NJ
CD 10 CLPP soil products
Illinois No. 6 (-80) toluene B, 10% NaOH, 50% C ₇ H ₁₅ J, 760 O
00 11 CLPP soil products
Illinois No. 6 (-80) toluene B, 5% NaOH, 40% CD ₃ J, 1200 _% O
CO 12th CLPP soil products
Illinois No. 6 (-80) toluene B, 10% NaOH, 50% (CH ₃ J ₂ SO ₄ , 380 _% 13th CLPP soil products
Illinois No. 6 (-80) toluene B, 10% NaOH, 50% CH ₂₁ Br, 731 _% 14th CLPP soil products
Illinois No. 6 (-80) toluene B, 5% NaOH, 40% C ₂ H ₅ J, 100 15th CLPP Soil Products-
Illinois No. 6 (-80) toluene T, 5% NaOH, 12% CD ₃ J, 250 % 16 CLPP soil products
Illinois No. 6 (-80) toluene T, NaOH, 12% CH ₃ J,

Table II continued

ο co o O NJ OJ

O OO O OO

at
game! Floor products
Coal liquefaction (DJ Solution
middle Catal
gate (2) 4% alkali (3) R ¹ X (4) i
314% 17th US Steel Full
Range Tar Xylenes A, 5% NaOH, 20% CH ₃ J, 330% 18th CLPP soil products
Wyodak toluene 5% NaOH, 12% CH ₃ J, 258% 19th CLPP soil products
Wyodak toluene τ, NaOH, 12% C ₄ H ₉ J,

Definition of symbols;

(1) the origin of the coal soil products is indicated; CLPP is coal liquefaction pilot plant; Mesh size given in brackets

(2) 3 is benzylhexadecyldimethylammonium chloride, A is ADOGEN 464, and T is tetrabutylammonium iodide. Weight percent based on carbonaceous material

(3)% by weight, based on metal base in water

(4)% by weight based on coal soil products

00

N) CD

cn ο

-Ρ-OO N)

In the case of CLPP bottoms, 3.5 alkyl groups for every 100 carbon atoms were added to the sample.
The H / C ratio in each sample increased depending on
the chain length in the added alkyl groups. the
O-alkylated soil products showed greater volatility and solubility in a variety of solvents and were richer in hydrogen and less viscous than the untreated soil products.

A comparison between untreated coal liquefaction bottoms and unmethylated coal liquefaction bottoms is shown in Table III.

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Table III

COMPARISON OF TREATED AND TREATED COAL SOIL PRODUCTS

O CO O O ro σ>

00 O 00

Traits, Coal-liquidity-
bcder.products O-ir.ethylated soil pro-
products from the coal supply
liquid Softening point (° C) 210 120 apparent viscosity
(Poise at 232 ° C) 185 19.5 apparent viscosity
(poise be: i 316 ° C) 25th 1 % volatile content 38 48 % oxidized 62 52 T ₁ (° C) 310 250 T _f ( ⁰ C) 600+
i
I. 580

co O

2950A82

Table Ijj shows a dramatic decrease in the softening point and viscosity of the coal bottoms, which means improved processability. The phase transition alkylation increases the volatile organic components in the liquefaction bottoms and lowers the boiling range (Ί \ or T _f ), ie more useful volatile organic carbon bottoms are obtained by distillation.

030026/0808 ORIGINAL INSPECTED

Claims (4)

li <ii'vVdAj \ I \ ^T · Ei ¹ ; ¹ ;, ·, ^ FAUTA &quot;"CU Uk. INU. F. HUF ΙΜΛΙ-1Ν (I '/ JO -l /.' I) · I ' ! il. ■ 11 · 'GW Γ 1 1: L · I) K. K ί. I ;. MAT. K. H OF PMAN N · I) I Fl.- 1 U GW It Il M i. »L Π .-! 'IC. V FHCIiSl.t Ii K. KtP. NA I. Π. HAIIStN ΑΚΛίι ι: UASikAiSK ι. (si ι κ ι:: i / .UL-j · o - ;. t ^; sj), hi:. ';. ium pi ■ iii.tif / N [ηκ) 9Π087. tpifx (■ / ■ · '/ ■ ,,',;? (ΐ / τΗϋ) 3 2 829 o / where ΕΧλ'ΟΝ PvIiSEARCIi AND ENGINEERING COMPANY, FLORIIAM PAm <, N.J. / US / i Procedure for Verbc-scr ung the Ei.rjonr.chaf · ion from KohJ.ovüril ür.s i. <! un '-; fjj'.rodul; Lon and -boden produ): th r λ τ γ: ν τ λ ν s ρ r ii c il j: ·; Method: - for improving the properties of Kohloverfl iirjy igunqsprodul.ten and Kohlebodcnprodukton by Sauer'Jtolf alkyl ation and / or Sauerster FACYL iorimg, characterized gekennseic- Ii η e t, dasi; one the. Cabbage base products treated with a solution (a) if a quaternary base of the formula R4QOR ", wherein each R is the same or different Group selected from C, - to oIv.m C ^, - Alky 1 and C, - to 030026/0808 ORlOlNAL INSPECTED οLvJH can be C ₂ aryl; Q denotes nitrogen or phosphorus, and K "denotes hydrogen, C. ..- to about C.sub.1 -alkyl, aryl, alkylaryl, arylalkyl or acetyl, and (b) at least one compound of the formula E ¹ X, in which K ^! cine C ₁ - to Cp ₀ -AlKyI or acyl group and X denotes a halide, sulfate, bisulfate, acetate or stearate, and borine X is bonded to a primary or secondary carbon atom. 2. The method according to claim 1, characterized in that R "denotes a Cj- to C. -AJ kylgruppe or hydrogen, that R denotes identical or different Cj- to Cg-alkyl groups, that R ¹ denotes a C 1- to C ^ - means inert hydrocarbon group and X means chlorine, bromine or iodine. 3. incident con according to claim 2, characterized in that X is chlorine, R ^{1 is a} methyl group; and Q is nitrogen. 4. The method according to any one of the preceding claims, characterized in that the amount at quatcrnJiror base the cloth iornc tr.ir, before η amount up to about 10 times the total number of acidic sites in the Koh1.efliis3igke.it or the coal soil product is equivalent to. ü. The method according to any one of the preceding claims, characterized in that R ¹ X in at least a stochioinctrischen amount, based on 030026/0808 ORIGINAL INSPECTED the number of acidic sites in the coal liquid odor dor Koh] floor products is available. Method according to one of the preceding claims, characterized in that the quaternary Salt dor formula K.QX with an alkali or Alkaline earth base of the formula MOR "with formation of the corresponding quaternary Dase, in which M is an alkali or alkaline earth metal, is reacted. Method according to one of the preceding claims, characterized in that the implementation is carried out catalytically. Method geinäsr; Claim 7, characterized in that g e k e η η ζ e i c h η e t that the amount dos quaternary salt <-o.no catalytic «size in the range from 0.05 to 10 Gew.S, based on the amount of coal. Method according to claim 6, characterized in that g e k e η η that the quaternary base is formed separately from the / dkylation or acylation reaction will. Method according to claim 6, characterized in that it is repeated at least once will. 030076/0 8