EA012243B1 - Depressant for highly paraffinic crude and oil products and process for preparing thereof - Google Patents

Abstract

The invention relates to methods of highly paraffinic crude transportation improving rheological properties thereof. The inventive result is aimed at improving depressant properties, reducing depressant effective concentration, flow and viscosity temperature loss of crude oil and oil products to be transported. The technical result is achieved by using a depressant being a product of polyoxyethylenesorbitan ester condensation with carboxylic acids anhydrides in the amount of 0.0005-0.50 mass %. The inventive method also provides its simplification. The method for manufacturing depressant for crude oils and oil products by condensing polyatomic alcohol with acid organic component in the presence of a catalyst characterized in that the condensation is carried out in the medium of aprotonic organic solvent with subsequent diluent addition, and as polyatomic alcohol ester there used polyoxyethylenesorbitan ester in the form of polyoxyethylenesorbitan mono- and trioleat, monolaurate or monostearate, in the form of the acid organic component – dianhydrides of aliphatic, alicyclic, aromatic tetracarboxylic acids, corresponding acids alkyl- and halo-containing dianhydrides of alicyclic tetracarboxylic acids. The depressant is used as a solution in the mixture of aprotonic organic solvent with alkylbenzene and pyridine.

Description

The invention relates to the field of chemistry of depressant additives for high-paraffin oils and petroleum products and is intended to reduce the pour point of high-paraffin oils and petroleum products, improve rheological properties during their transportation.

Oil with a high paraffin content is characterized by a high pour point and for its transportation through the pipeline or in tanks, additional measures must be taken to give the oil the necessary fluidity.

Widespread use for reducing the viscosity of oils and petroleum products received depressant additives.

Known depressant additives in the form of mixtures of organic compounds. The multicomponent composition includes a mixture of synthetic anionic and nonionic surfactants, ethoxylated esters of phosphoric acid, hydrocarbon solvents of 50-90 wt.%, Aliphatic or aromatic alcohols or products containing them - 10-50 wt.%. (RF patent 2176656, IPC C 09K 3/00, E 21B 37/06). The effectiveness of the additive in reducing the pour point is insufficient.

It is known to use an additive that is a surfactant with hydrophobic and hydrophilic groups. The additive is an ethoxylated fatty acid fraction C ₁₇ -C ₂₀ (Aut. St. USSR 273356, IPC E 176 1/16, 1970).

The closest in the invention according to the technical essence and the technical result achieved, are a depressant additive and a method for its preparation, according to Auth. USSR 1049524, IPC С 10М 1/26, С 10Ь 1/19, 1983. The prototype depressant additive is the product of the interaction of synthetic C21-C25 fatty acids with pentaerythritol in the presence of zinc oxide. The resulting esters are further reacted with phthalic anhydride in the presence of an α-zinc oxide catalyst. Additive in oil is introduced in an amount of 0.5-2.0 wt.%, While the depression of the pour point reaches 37-38 ° C. However, there is no information on the rheological properties of depressed oil. In addition, the disadvantage of the additive according to the prototype and the method for its preparation is the difficulty of obtaining the additive - two-stage, high reaction temperature - 170 ° C, the use of an azeotropic solvent, the need for centrifugation and distillation of the solvent.

The task of the invention is to develop an effective and affordable depressant additives for high-paraffin oils and a method for its production.

The technical result of the invention is to improve the properties of a depressant additive: reducing the effective concentration of a depressant additive, pour point, kinematic and effective viscosity of high-paraffin oils.

Technical result is achieved depressant additive, which is a condensation product of polyoxyethylene sorbitan ester (polyoxyethylated polyols, wherein the polyol is the function of anhydrosorbitols mixture) of the formula (OH) n A (OC ₂ H _{4) x} OH (1) with anhydrides of carboxylic acids, exhibiting surface active properties.

The technical result of the invention in terms of the method is its simplification.

To obtain depressant additives, sorbitan (polyoxyethylene) mono and trioleate in the form of commercial products of the brand TWIN-80, TWIN-85, respectively, sorbitan (polyoxyethylene) monolaurate in the form of the commercial product TVIN-20, sorbitan (polyoxyethylene) monostearate in the form of commercial product TWIN-60.

Physico-chemical characteristics of polyoxyethylene sorbitan esters are presented in table. 1. Table 1. Physico-chemical characteristics of commercial products of brands "Twin" *

The name of indicators Twin 20 Twin 60 Twin 80 T vin-85 Chemical product name Sorbitaibns (polyoxyethylene) monolaurate Sorbitanbis (polyoxyethylene) monostearate Sorbitanbis (polyoxyethylene flax) monooleate Sorbitan (polyoxyethylene flax) -trioleate Gross formula C 54 H 108 024 C 60 Η 118 024 C60H 116 024 C 72 H 132 014 Molecular Weight 1140 1222 1220 1220 The content of the main substance,% 100.0 96.0 98.0 98.0 Moisture contents,% less than 0.2 2-4 1-2 1-2 Appearance Light yellow oily liquid Light yellow oily liquid OILY LEMON to amber color with a faint characteristic odor Amber-colored oily liquid with a faint ¹ characteristic odor Density, g / cm ' 1.06 1.07-1.10 1.06-1.10 1,033 -1,13 The temperature of the capture, ⁰ C - 22-24 • Viscosity, Pa.s 0.24-0.70 0.40-0.60 0.24-0.26 - Solubility SS14 CC14, distilled water, benzene Methanol, ethanol, toluene, ethyl cetate Diesel fuel, DMF,

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DMAA, in a mixture of these solvents with benzene or toluene, xylene, ogre, in benzene HLB (hydrophilic lipophilic balance) 16.7 14.9 15.0 11.0 Acid Number (CN) mg KOH / g 0-2.0 4.0 The number of saponification (HO), mg KOH / g 45-55 45-55 45-60 - CMC (critical micelle concentration) 106 μmol / l 0.06 g / l

* Surfactants. Reference book / Abramzon A.A., Bocharov V.V., Gaevoy G.M. and etc.; under the editorship of A. Abramzon and G.M. Gay. L., Chemistry, 1979, 376 p. Surfactants of foreign firms. M., Central Research Institute of Information and Technical and Economic Studies of Non-Ferrous Metallurgy, 1977. 51 p. Schönfeld N. Ethylene Oxide Surfactants. Per. with him./ Ed. N.N. Lebedev, ed. 2nd, M. Chemistry, 1982, 752 pp.

Depressor additives are obtained by condensation of acid anhydrides (aliphatic, alicyclic and aromatic) of reactive purity with physicochemical properties corresponding to literary sources (* Zhubanov B.A., Arkhipova I.A., O.A. Almabekov. New heat-resistant heterocyclic polymers. Alma Ata, Nauka, 1979, 252 pp.)

As the tetracarboxylic acid dianhydrides, butanetetracarboxylic acid dianhydride, pyromellitic acid dianhydride, tricyclo- (4,2,2,0 ^2,5 ) -dec-7en-3,4,7,8 tetracarboxylic dianhydride and its alkyl and halide derivatives are used ( table 2).

Table 2. Characterization of acid anhydrides *

Acid Anhydrides Gross formula Molecular weight Melting point, ° С Dissolve- the bridge Pyromellitic Acid Dianhydride SHONGOB 218 286 DMFA, DMAA, DMSO Tricyclo (4.2.2.0 ^{2> 5} ) -dec-7ene3,4,7,8-tetracarboxylic acid dianhydride C ^ nuob 274 354 DMF DMAA, DMSO cresol, phenol Tricyclo Dianhydride - (4,2> 2, (g ^{, 5} ) -dec-7en-7- SYNDOBS! 309.5 290-295 DMFA, DMAA, DMSO

3,4,7,8-tetracarboxylic acid chlorine Tricyclo - (4,2,2,0 ^{2 /} ) -dec-7en7-isopropyl tetracarboxylic acid dianhydride SRNcOb 314 242 DMF DMAA, DMSO, cresol, phenol Benzophenone tetracarboxylic dianhydride C | ? H 6O7 322 265 DMFA, DMAA, DMSO Butanetetracarboxylic Dianhydride sciOb 196 162 Nitrobenzene, pyridine, quinoline, cresol, phenol, DMF, DMAA, DMSO

A depressant additive is obtained in one stage.

In a reactor equipped with a stirrer, a refrigerator, a hatch for dry products and fittings for introducing solvents and reagents, tetracarboxylic acid dianhydride is dissolved in Ν, Ν dimethylformamide at 60-70 ° С.

Polyoxyethylene sorbitan ester in the amount of 3.8-4.0 mol per 1 mol of dian is gradually fed to the solution of dianhydride in ^ Ndimethylformamide from the measuring device while the stirrer is working.

- 2 012243 tetracarboxylic acid hydride, the reaction solution is homogenized by stirring the solution and the catalyst is added in an amount of 2 moles (pyridine). The temperature was raised to 140 ° C and maintained at this temperature for 4 hours with continuous stirring and temperature control. Solvent vapors are trapped in a condenser (refrigerator) and drained back into the reactor. The process can be carried out in an inert gas stream. After completion of the condensation process, a diluent (o-xylene, toluene) is supplied from the measuring device at a mass ratio of solvent: diluent equal to 1: 0.5, the mixture is stirred for another 1 hour, and then the diluent is further introduced. The ratio of solvent: diluent becomes equal to 1: 1.

The total duration of the process is 5.5 hours. The finished solution of the oligomeric depressant additive is cooled by supplying coolant to the reactor jacket, the reaction product is poured into the storage tank through the bottom fitting of the reactor, and it is fed to the filter to remove mechanical impurities using a pump. Quality control is the transparency of the oligomer solution and compliance with the standards (table. 3).

Example 1. 0.218 kg of pyromellitic dianhydride is dissolved in a reactor in 10 l of Ν dimethylformamide at a temperature of 60-70 ° C. Then, 0.392 kg of pyridine and 4.635 kg of sorbitan (polyoxyethylene) trioleate (TWIN-85) are added to the reactor. The reaction solution is heated to 140 ° C with constant stirring and maintained at this temperature for 4 hours, then 5 L of o-xylene is added, kept at 140 ° C for another 1 hour and 5 L of o-xylene are additionally added. The total duration of the process is 5.5 hours. The resulting oligomer solution is used as the finished commodity additive Csp1g-4 for high-paraffin oils.

Mass fraction of the main substance in the range of 19-21%. The molecular weight of the oligomer is 5098 cu, pH-6.95, density at 20 ° C - 0.948 g / cm ³ .

Example 2. According to example 1, 0.274 kg of tricyclo- (4,2,2,0 ^2,5 ) -dec-7en3,4,7,8-tetracarboxylic acid dianhydride is condensed with 4.635 kg of sorbitan (polyoxyethylene) trioleate (TWIN-85 ) in the presence of 0.392 kg of pyridine. The resulting oligomer solution is used as the finished commodity additive Csp1g-5. Mass fraction of the main substance in the range of 19-21.5%. The molecular weight of the oligomer 515 4.u.; pH 6.95; the density at 20 ° C is 0.941 g / cm ³ .

Example 3. According to example 1, 0.196 kg of butanetetracarboxylic dianhydride is condensed with 4.635 kg of sorbitan- (polyoxyethylene) trioleate (TWIN-85) in the presence of 0.392 kg of pyridine. The resulting oligomer solution is used as the finished commodity additive Csp1g-6. Mass fraction of the main substance in the range of 19-21.5%. The molecular weight of the oligomer is 5076 cu; pH 6.95; the density at 20 ° C is 0.935 g / cm ³ .

Example 4. According to example 1, a condensation of 0.309 kg of chlorine-containing dianhydride of tricyclo (4.2.2.0 ^2.5 ) -dec-7en-3,4,7,8-tetracarboxylic acid with 4.635 kg of sorbitan (polyoxyethylene) trioleate ( TWIN-85) in the presence of 0.392 kg of pyridine. The resulting oligomer solution is used as the finished commodity additive Csp1g-7. Mass fraction of the main substance in the range of 19-21.5%. The molecular weight of the oligomer 5189.5 cu; pH 6.95; density at 20 ° С-0.938 g / cm.

The depressant additives based on TWINA-85 and pyromellitic and tricyclo (4,2,2,0 ^2,5 ) -dec-7en-3,4,7,8-tetracarboxylic dianhydrides are characterized by the physicochemical properties shown in the table. 3.

Table 3. Physico-chemical characteristics of oligomeric depressant additives Csp1g-4. Ssp1g-5

Name indicators Norm Oep1g -4 Norm 6ep (g -5 Test method, GOST (A8TM) Outside view Light yellow to amber clear liquid Lemon to amber clear liquid Visually Density at 20 ° C 0.948 g / cm ¹ 'O ^ Gg / cm ³ 3900.2477-65 (ϋ-1298) Mass fraction main substance,% within 19-21,5 19-21,5 PH 6.95 6.95 Pour point, ®С Below minus 30 Below minus 30 20287-91 (0-97) Kinematic viscosity 2.85 mm ² / s (cST) 2.65 mm ² / s (cST) 33-2000 (0-445- 96) Molecular mass 5098 cu 5154 c.u. Mass fraction mechanical impurities Lack,% Lack,% 2477 Effective depression Tpt when entering in the amount of 0.01- 0.5 wt.% Not less than 15-20 ° С Not less than 15-20 ° С (D97D5853)

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The effectiveness of the depressant additive is determined on high-paraffin oils of the fields: Kumkol, Konys, Zhetybai. Akshabulak, Aryskum, Buzachi, Mangyshlak, Uzen, or mixtures thereof with different physicochemical characteristics (Table 4).

Table 4. Characteristics of high-paraffin oil samples

Physicochemical characteristics of oils Kumkol Konys Kumkol: Akshabu varnish 60:40 Zhetybai Mangysh lakish Buzachi: Mangysh Lak Density, g / cm ³ Temperature 0.817 0.822 0.821 0.855 0.860 0,900 yield loss, ° C + 12.0 +21.0 +12.0 +33 +27 +24 Content, wt.% Paraffin 14.44 26.7 14.41 19.9 19,4 16.5

The introduction of a depressant additive is carried out as follows: 0.005-0.50 wt.% Depressant additives are introduced into highly paraffin oil in the form of solutions in organic solvents. High-paraffin oil is heated before and after the introduction of the depressant to temperatures from 50 to 90 ° C and stirred at this temperature for at least 20 minutes and then cooled at a speed of 0.5 ° C / min to 25-30 ° C.

The introduction of a depressant additive significantly reduces the temperature of the fluidity loss of oil and improves the rheological characteristics of high-paraffin oil.

The temperature of the fluidity loss of high-paraffin oil before and after the introduction of a depressant additive into it is determined according to GOST 20287-91.

The effective viscosity is determined on a rotational viscometer type DR 8e1es1a brand 8TΌΙΟΙΤ system cylinder-to-cylinder.

Inhibition of asphalt-resinous and paraffin deposits (paraffin deposits) was studied by the cold rod method (s1b 1shdeg) on a special installation simulating the deposition process of paraffin deposits on the main pipeline. The measurements are carried out in a cylindrical thermostatic stainless steel beaker with a volume of 500 ml with stirring with a magnetic stirrer. The oil volume was 250 ml. A cooled rod made of stainless steel is placed in the glass, in which a constant temperature is maintained. The temperature of the rod corresponded to a temperature of 5 ° C. The oil mixture had a temperature of 30 ° C. Precipitation is carried out for 3 hours. After that, the rod is removed from the glass and immersed in acetone to flush the oil. Precipitated paraffin deposits are removed mechanically and heated to 70 ° C with toluene. The mass of paraffin is determined after distillation of toluene.

Experimental studies of the stability of the action of a depressant additive over time are carried out according to the following procedure: a calculated amount of a depressant additive is injected into a two liter sample of high-paraffin oil. The flask with the resulting mixture was placed in a thermostat with a temperature of 60 ° C and, with stirring, the sample was thermostated for 30 minutes. Then the sample is cooled at a speed of 0.5 ° C / min to 25-30 ° C, poured into 20 flasks and placed in a thermostat with a temperature of 0 ° C, where the samples were for a predetermined time. At certain intervals, one of the samples with the test oil is removed to determine the pour point and effective viscosity.

Information confirming the possibility of carrying out the invention is disclosed in examples 1-4 and table. 5-11.

From the above table. 5-11, it follows that high-paraffin oil with oligomeric depressant additives is characterized by improved low-temperature and rheological properties.

The analysis of the data in table 10 indicate that the stability of the depressant effect of oil is maintained for 30 days.

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Table 5. Change in temperature of yield stress (Tp) of samples of individual oils and oil mixtures after heat treatment and input depressor Csp1g-4

Oil Oil processing temperature, ° С The temperature loss of fluidity, ° C The content of Sep1g-4, wt.% 0 0.005 0.010 0.015 0,020 0,040 Raw Aryskum 21 Aryskum heat-treated 80 3 - - - - - Additive treated Aryskum 80 0 -nine -12 -12 Akshabulak raw eighteen Akshabulak heat-treated 65 12 - - - - - Akshabulak treated with additive 65 0 -nine -12 -nine Akshabulak-Kumkol (11:89 volume.%) Treated with the additive 65 12 -nine Akshabulak-Kumkol (30:70 vol.%), Treated with the additive 65 12 -nine Konis raw 21 Konys heat-treated 80 12 Cony processed additive 80 +3 +3 0 +3 - Buzachi-Mangyshlak (20:80 volume.%) Treated with the additive 90 27 nine * Uzen.obrabotannaya additive 90 thirty eighteen**

* additive content of 0.5 wt.%; ** additive content of 0.1 wt.%.

Table 6. The change in temperature of the loss of fluidity of the oil mixture Buzachi-Mangyshlak (20:80 vol.%) After heat treatment and the introduction of additives Sep1g -5

№№ Sample Name Tpt, ° C one Buzachi-Mangyshlak raw 24 2 Buzachi-Mangyshlak (heat-treated at 80 “C) 12 3 Buzachi-Mangyshlak with Oep1g-5 0.1 wt.% nine 4 Buzachi-Mangyshlak with СеШг -5 0.5 wt.% 3

These tables confirm the properties of the claimed depressant additives.

The rheological properties of the Kumkol-Akshabulak oil mixture are improved by treatment with their additives.

The optimal concentration of additives Sep1g-4. Sep1g-5 and Sep1g-6 is 0.01 wt.%. With a decrease in the concentration of the introduced additive to 0.005 wt.% And an increase to 0.015 wt.%, The rheological characteristics of the oil mixture slightly deteriorate. When comparing the effectiveness of the influence of various additives on the rheological parameters of the Kumkol-Akshabulak oil mixture (60:40 vol.%), Sep1g-4 and Sep1g -5 additives are the best.

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Table 7. Rheological characteristics of the Kumkol-Akshabulak oil mixture (60:40 vol.%) Before and after treatment with Sep1g-4 depressant. Shear rate 5s ^-1

The concentration of additives, wt.% Temperature, ° С ' Shear stress, Pa Effective viscosity Pa.s 0 0 75 thirteen 0.005 and 0.01 0.010 0.1 0.08 0,020 5.1 0.4 0 -5 160 35 0.005 2.7 0.65 0.010 0.6 0.09 0.020 4.9 and

Table 8. Rheological characteristics of the Kumkol-Akshabulak oil mixture (60:40 vol.%) Before and after treatment with depressant Csp1g-5. Shear rate 5s ^-1

The concentration of additives, wt.% Temperature .С [1tension shear. Pa Effective viscosity Pa * .s 0 0 75 fifteen 0.005 0.35 0.01 0.010 0.001 0.009 0.020 0.2 0.4 0 -5 165 32.5 0.005 21 4.1 0.010 1.0 0.1 0,020 7.5  -

Table 9. Rheological characteristics of Zhetybai oil before and after treatment with depressant Csp1g-5 at 90 ° C. Shear rate 5 s ^-1 .

The concentration of additives, wt.% Temperature ° C 1 shear conjugation, 11a Effective viscosity Pass 0 twenty twenty twenty 125 25 0.1 40 8 0.5 95 17..5 0 12.5 12.5 K) 11c will be able to measure. Solid oil 1 [C manages to measure. Solid oil 0.1 150 31.5 0.5 200 40

Table 10. Change in temperature of loss of fluidity of the Kumkol-Akshabulak oil mixture (60:40 vol.%) In the presence of Sep1t-4 additive (0.01 wt.%)

Sample ^Yield temperature, ^ϋ С 1 day 3 day 5 day 10 day 20 day 30 day Kumkol-Akshabulak (heat treated at 60 ° C) 6 6 6 6 6 nine Kumkol-Akshabulak with an additive (0.01 wt.%) -6 -6 -6 -3 -3 0

The inhibitory ability of the oligomeric depressant additive Sep1t-4 is presented in table. eleven.

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Table 11. The effect of the depressant additive Sei1g-4 on the inhibition of the paraffin deposition process

Duration, day Crude oil blend Additive-treated oil blend Oep1g-4 (0.01 wt.%) t, g Number of paraffin from oil,% The degree of inhibition,% t, g Number of paraffin from oil,% The degree of inhibition,% one 9.2 4,5 0 3.6 1.8 60.9 3 9.2 4,5 0 3.0 1,5 67.4 5 9.2 4,5 0 3,1 1,5 66.3 10 9.2 4,5 0 3.2 1,6 65,2 twenty 9.2 4,5 0 3,1 1,5 66.3 thirty 9.2 4,5 0 3.3 1,6 64.1

The information given in table. 11, confirm that the degree of inhibition of asphaltene paraffin deposits relative to the crude Kumkol-Akshabulak oil mixture (60:40 vol.%), When treated with Sei1g-4 reagent increases and is 60-67%.

Thus, the use of depressant additives Sei1g-4 and Sei1g -5, according to the invention, can improve the productivity and reliability of oil pipelines, reduce operating costs for pumping oil, reduce the temperature limit of pumping, which is especially important when transporting high-paraffin oils in the autumn-winter period.

The consumption of the depressant additive according to the invention compared with the additive of the prototype is reduced to 0.01 wt.%. while achieving high efficiency.

Depressor properties are characterized by indicators: depression of pour point, 18-24 ° C, with a significant improvement in rheological characteristics. The effective viscosity of oils is reduced, on average, by two orders of magnitude.

The use of additives Sei1g-4, Sei1g-5 does not have any technical limitations and technological difficulties, since depressant additives are organic compounds that are easily combined with oils and oil products or soluble in organic solvents that are also readily soluble in oils and oil products.

The claimed method in comparison with the prototype is characterized by ease of implementation: does not require distillation of the solvent; the condensation temperature is 30 ° C lower than the prototype method; there is no distillation of the azeotrope, the allocation of additives and its purification.

Claims (8)

CLAIM 1. Depressor additive for high-paraffin oils and petroleum products based on a condensate of organic polybasic compounds, characterized in that it is a condensation product of an ester of polyoxyethylene sorbitan with an aliphatic, alicyclic, aromatic tetracarboxylic acid dianhydride, alkyl and halide dicarbonic acid dichloride. 2. The depressant additive according to claim 1, characterized in that the dianhydride is pyromellitic or alicyclic tricyclo (4,2,2,0 ^2,5 ) dec-7-en-3,4,7,8-tetracarboxylic acid dianhydride. 3. The depressant additive according to claim 1, characterized in that the polyoxyethylene sorbitan ester is a polyoxyethylene sorbitan mono- or trioleate, a polyoxyethylene sorbitan monolaurate or monostearate. 4. A method of producing a depressant additive for high-paraffin oils and oil products by condensation of a polyhydric alcohol ester with an acidic organic component in the presence of a catalyst, characterized in that the condensation is carried out in an aprotic organic solvent followed by the addition of a diluent, polyoxyethylene sorbitan ester is used as a polyhydric alcohol ester, and as an acidic organic component - dianhydride of aliphatic, alicyclic, aromatic tetracarbon hydrochloric acid, alkyl- and halide-containing alicyclic tetracarboxylic acid dianhydride. 5. The method according to claim 4, characterized in that the polyoxyethylene sorbitan ester is a polyoxyethylene sorbitan monoil or trioleate, a polyoxyethylene sorbitan monolaurate or monostearate. 6. The method according to claim 4, characterized in that Ν, Ν dimethylformamide, dimethyl sulfoxide, No. methylpyrrolidone, ^ No. dimethylacetamide are used as the organic solvent. 7. The method according to claim 4, characterized in that alkylbenzenes, in particular o-xylene, toluene, are used as a diluent. 8. The method according to claim 4, characterized in that tertiary amines, in particular pyridine, are used as a catalyst.