CS256170B1 - Process of processing trace materials - Google Patents

Abstract

The method of processing trace materials, especially difficult to decompose trace emulsions from refinery and petrochemical processing of crude oil, containing 3 to 75% water and mechanical impurities, is carried out in such a way that 0.02 to 2 parts by weight of a by-product from the catalytic oxidation of cyclohexane to cyclohexanol and cyclohexanone, isolated from the "hydrolysis" stage as a distillation residue (acid number = 100 to 350 mg KOH/g; saponification number = 250 to 500 mg KOH/g) and/or a by-product from organochemical production containing at least one C1-C1 carboxylic acid, is added to 1 part by weight of the trace material, while stirring and at 10 to 98 °C. The trace material modified in this way is separated. The lower water layer is discharged into wastewater, the middle and/or upper organic layer is either directly burned, mixed with heating oil, or fed into primary oil processing.

Description

The invention relates to a process for the treatment of trace materials, in particular hardly degradable slurry emulsions, containing products from refining and petrochemical oil processing, with variable water content, organic and inorganic components, including mechanical impurities and by-product utilization, from high-throughput petrochemical processes.

In oil refineries and petrochemical plants, by-products are usually processed from each set of production or even individual ones, and also treated, whether or not they are processed. at least partially purify the wastewater before it is discharged for final treatment or to public streams. In some cases, however, water with varying properties is drained together from a larger set of production or the entire petroleum and petrochemical production plant. The quality and physicochemical properties of the waste lines depend on the properties of the substances, soluble, emulsified or dispersed therein. Thus, the amount of hydrocarbon and other organic fractions that enter the waste line also depends on the manner and depth of oil processing. In plants with a fuel-oil processing scheme, this is usually up to 2% by weight, occasionally more for feed oil. In petrochemical plants, various by-products and occasionally degraded portions of the main products, such as fractions from catalytic and destruction processes, as well as various chemicals with an alkaline or acidic nature, enter the waste lines. Such are high pH alkaline solutions, sodium sulfide, aluminum chloride, aluminum chloride complexes, ion exchange water regeneration, and the like. Other waste impurities include sand, clay particles, soluble mineral salts, rust and various mechanical impurities from cleaning equipment, storage tanks as well as polymer granules. In order to avoid operational difficulties, it is essential to separate the waste lines from the various production lines and to clean them in separate circuits.

However, if they encounter water with different physicochemical properties and water with hydrocarbon and other organic fractions in the sewage collection system, whether inadequate construction of separate collection circuits or at different technological stops, charges or emergency interconnections, more or less is formed stable emulsions. A special case is the formation of a hardly degradable ivory emulsion. Storage of slurry emulsions in tanks often further increases their stability, has a structural viscosity and unsatisfactory flow and other physical properties.

The ivory emulsions are partially processed by settling heating in tanks. After a few days of standing, the lower water layer is drained and the upper hydrocarbon layer is drained. The middle layer of slop remains in the tanks. When hardly degradable ivory emulsions are formed, hot separation does not lead to the desired emulsion decomposition. Known emulsion decomposition techniques using tone and non-tone type demulsifiers at different pH, multivalent ion electrolytes, ion adsorption, electrostatic pole and centrifugation do not give satisfactory results. Apparently also because the proportion of components stabilizing ivory emulsions is variable. Therefore, the use of such slopes as an energy fuel requires specially adapted combustion equipment, since the slurry emulsions differ significantly in several basic quality parameters from commercial fuel oil. They have a structural viscosity, unsatisfactory flow properties, a variable water content and water-soluble or dispersed substances and, depending on the water content, a variable reduced calorific value. In storage tanks, they are located in non-homogeneous layers with varying properties and contain an increased content of mechanical impurities, which, by their size, often exceed the common nozzle orifices in oil burners. Progress in solving this problem is the method of complex processing of slop emulsions according to Czechoslovakia. No. 212 353, consisting of intensive mixing of slopes at a temperature of 20 to 95 ^° C with the addition of 0.01 to 5 wt. acids (sulfuric acid, nitric acid, acetic acid, citric acid, alkylsulfonic acids) capable of forming, with the basic constituents of the slurry emulsions, water-soluble salts or metal soaps and / or with the addition of a substance having dispersing properties in an amount of 0.01 to 3% by weight; after separation of the mechanical impurities, the emulsion is burned directly after homogenization, or is fired directly after homogenization or mixed with fuel oil in a weight ratio of 1: 1 to 1: 100, or the modified ivory emulsion after homogenization is allowed to separate by settling. The v / o emulsion predominant top layer returns to the primary oil processing, the o / v or mixed type predominant middle layer is burned directly or after mixing with fuel oil, and the bottom layer consisting predominantly of water is drained into chemically contaminated leads . However, the disadvantage of such processing of difficult-to-degrade emulsions is that they only run off in such a way that virtually no or only partial drainage of the emulsions occurs and so much emulsion and thus water remain in the hydrocarbon materials, which complicates their use alone or in combination with heavy fuel oils. in which not only the content of the carbon constituents varies, but even stratification may occur. Such emulsions in principle cannot be returned to the primary processing of the oil. In addition, additives of acids, especially hydrochloric acid), but also others cause corrosion of storage, handling and combustion plants. Therefore, they require anti-corrosion additives or other corrosion inhibitors of the equipment.

In contrast, a process for the treatment of trace materials, in particular difficult-to-degradable trace emulsions from refining and petrochemical processing of petroleum containing from 3 to 75% by weight. water, with a mechanical impurity content of 0.1 to 25 wt. is realized so that per 1 wt. 0.02 to 2 wt.% of the trace material is added in one portion or in portions with stirring at a temperature of 10 to 98 ° C. parts of the by-product from the catalytic oxidation of cyclohexane to cyclohexanol and / or cyclohexanone, isolated from the 'hydrolysis' stage as a distillation residue after separation of a substantial part of water with an acidity of 100 to 350 mg KOH / g, saponification number 250 to 500 mg KOH / g % hydroxyl number 2 to 8 wt. OH and a bromine number of 5 to 35 g Br / 100 g and / or a by-product from organoclemiic products containing at least one carboxylic acid C 1 to C 1 and the trace material thus modified are separated by centrifugation and / or settling.

An advantage of the process for the complex treatment of trace materials, in particular the poorly degradable trace emulsions of the present invention, is the deep drainage of the trace emulsions or trace materials, which has not been accomplished by any demulsifiers or known slop dewatering techniques. The substantially dewatered material obtained, optionally containing a small amount of emulsified water (usually below 5%) and additionally containing a portion of the by-product, from the catalytic oxidation process of cyclohexane to cyclohexanol and cyclohexanone with a calorific value of about 29 MJ / kg Such material is well miscible with other hydrocarbon fuels, mainly due to good dewatering, but also with the addition of semi-esters, esters, lactones, carboxylic acids Cs to Ce and other oxygen-containing organic compounds. The compounds together with the acidic constituents present effectively disrupt stable trace emulsions and significantly reduce the structural viscosity of the fuel formed, or the fuel component with improved leakage or processed oil. also a beneficial catalytic effect on vision.

By-product from the process of catalytic oxidation of cyclohexane to cyclohexanol and cyclohexanone isolated as a distillation residue (referred to as MEK), freed of some of the water from the hydrolysis column of the cyclobexanol production plant, respectively. cyclohexanone has an acid number in the range of 100 to 350 mg KOH / g, but most often 250 ± 30 mg KOH / g. Saponification number 250 to 500 mg KOH / g, but most often 400 ± 30 mg KOH / g; 4-10% by weight of water; % bromine number 5 to 35 g Br / 100 grams and hydroxyl number 2 to 8 wt. OH. As a rule, it contains below 0.02 wt. cobalt in the form of cobalt compounds as well as trace amounts of other metals.

In the case of a by-product from organochemical products containing at least one C 1 to C 4 carboxylic acid, the distillation residue from acetic acid recovery, resp. rectification of vinyl acetate in a vinyl acetate production plant by catalytic addition of acetic acid to acetylene containing from 60 to 100% a mixture of acetic acid, acetic anhydride and ethylidenediacetate. In such a distillation residue it is most common ^! e 65 ± 10% acetic acid, 12 ± 5% acetic anhydride, the remainder to 100% being ethylidene diacetate, vinyl acetate, vinyl acetate polymers and the like. It also includes the distillation residue from acetic acid production, as well as mixtures of formic, acetic and propionic acids from the scrubbing heads of the cyclohexanone production plant.

The process according to the invention is preferably carried out in a discontinuous manner, but can also be carried out semi-continuously and continuously.

Further details of the method of complex processing of trace materials as well as other advantages are evident from the examples.

Example 1

By analyzing two samples of the by-product from the catalytic oxidation of cyclohexane to cyclohexanol and / or cyclohexanone, isolated at different times as the distillation residue from the hydrolysis column boil after separation of a substantial part of the water (e.g. column D 110) and cyclohexanone, referred to as · MEK (1) and MEK (2), found the following values [in brackets refers to MEK (2)]: water = 6.9 (6.1) wt%; acid number = 256.3 (253.8) mgKOH / g; saponification number = 412.8 (403.7) mgKOH / g; OH = 4.7 (4.3) wt%; bromine number = 23.1 (21.8) g Br / 100 g; density pti 20 ^C (d4 ²⁰ ) = 1 104 (1 109) kgm ³ ; at 30 ° C) (d 4 ³⁰⁾ = 1100 (1086) kgm ~ ^3; at 40 ° C = 1087 (1,078) kgm- ³ ; density at 50 ° C (d 4 ⁵⁰⁾ = 1079 (1070) kgm ^"3; the dynamic viscosity at 20 ^C C 268.9 (233.2) mPas. with; at 30 ° C = 124.4 (126.4) mPa. with; at 40 ° C = 64.8 (71.4) mPa · s; at 50 ° C = 38.7 (43.1) mPa · s; cobalt content in the form of compounds = 0.01 (0.01) wt.%, ash = 0.05 (0.04) wt. It consists of a mixture of monocarboxylic and dicarboxylic acids, hydroxy and keto acids, their cyclohexyl esters. Furthermore, lactones are present in monomeric form, but also dimers and polymers. Monocarboxylic acids (butyric, valeric and caproic acid), di, carboxylic acids (succinic, glutaric, adipic) and hydroxy acids (delta-hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid) were identified. Then the esters of said and other acids (cyclohexyl valerate; cyclohexyl caprone; cyclohexyl glutarate; cyclohexyl adipane). In addition, they contain admixtures of cobalt, iron, nickel, titanium and zinc compounds.

Samples of trace materials A, B, C, the characteristics of which are given in Table 1, are taken from the three tanks of the refinery-petrochemical plant.

Table 1

Labeling Trace Material Composition Trace Material Properties

samples water content (% by weight) content of mechanical impurities (O / O mass) A 32 8.3 B 67 17.0 C 12.3 5.1

Slurry consistency, inhomogeneous layers, mixed type emulsion

Brown villous emulsion, structural viscosity, non-homogeneous O / W emulsion layers

Coarse-dispersion emulsion, pH = 6.8, with an emulsion predominating v / o

With vigorous stirring and at a temperature of 48 ± 2 ° C, 1 wt. 0.15 wt. parts of the distillation residue (MEK 1) and after 10 min. stirring was stopped. The ivory material was divided into 3 layers, the lower layer consisting essentially of an aqueous layer containing

86.3% of all water derived from trace material but also from the added MEK-1 component. Central! the layer consisted mainly of added MEK-1, with residual water and hydrocarbons with a net calorific value of 32 MJ / kg and the upper layer consisted mainly of lower MEK-1 hydrocarbons, which are both a suitable fuel, a heavy fuel oil component and a primary oil feed component .

The sample of trace material B was divided into 3 parts. To the first part of the sample, to 1 wt. 0.20 wt. a portion of the distillation residue (MEK-2); to the other to 1 wt. parts added 1 wt. part MEK-2 and the third to 1.5 wt. of MEK-2. All 3 samples were vigorously stirred at 88 ± 5 ° C for 15 min. Then stirring was stopped ¹ and the samples were stratified. The first sample was divided into 3 layers, with 87.9% of all water from the system in the lower water layer, the second and third being divided into only two layers, the lower one being up to 90.1 and 90.1% respectively. 91.2% of all water from the systems and the top was a substantially low-viscosity organic phase, which was used as a component of not only heavy but also light fuel oil. To the third trace material sample C, to wt. 0.06 wt. After 20 min. With vigorous stirring at 64 + 3 ° C, the sample was allowed to stratify. Three layers were formed, the smallest bottom layer containing 82% of all the water supplied to the system which was discharged for purification. The middle and top layers were similar in composition to the middle and top layers obtained from the sample of trace material A.

Example 2

Κ 1 wt. % of the trace material containing a hardly degradable emulsion and having a total water content of 34.2% by weight. and 9.1 wt. of mechanical impurities which were separated by filtration were added 0.05 wt. of MEK-1. After 20 min. mixing and © cooled! at 24 ° C, the obtained material was layered by sedimentation into a lower, essentially aqueous layer consisting of 90.5% of trace water and MEK 1. The upper, essentially organic low-viscosity layer was formulated with a heavy or even light heating It also boils with a suitable fuel mainly instead of a heavy fuel oil, and also in a 1: 1 weight ratio with heavy fuel oil, which has also improved flow properties and lowered the freezing point.

Example 3

The procedure was similar to Example 2, except that the mechanical impurities were removed from the individual layers after separation. The mechanical particle separation rate is almost twice as high as in Example 2. Example 4

Κ 1 wt. % of the trace material containing a hardly degradable emulsion having a total water content of 34.2% by weight. and 9.1 wt. 0.2% by weight of mechanical impurities was added with vigorous stirring at 66 ± 3 ° C. parts of MEK-1 and 0.2 wt. parts of the distillation residue from acetic acid recovery from vinyl acetate production plant, containing

73.1% acetic acid, 13.3% acetic anhydride, 11.3% ethylidene diacetate, admixtures of resins and vinyl acetate. After 20 min. After intensive mixing, the modified ivory material was allowed to sediment. Two layers were formed, the lower-aqueous layer being drained into the sewage of chemical water and the upper one was stripped and filtered of mechanical impurities and used as fuel instead of heavy fuel oil.

Example 5

The procedure is similar to Example 4 except that 0.2 wt. parts of a mixture of formic, acetic and propionic acids in the form of an aqueous solution of scrubbing acid waters from a cyclohexanone plant (acid scrubbing waters from the DS-104 separator had the following composition: formic acid = 3.8 wt.%, acetic acid = 1.5 wt. propionic acid = 1.6% by weight, cyclohexane = 0.1% by weight, cyclohexanol = 1.15% by weight, water = 92.4% by weight. 14% lower After removing mechanical impurities by filtration, the top layer was used as fuel oil.

Example 6

The procedure is similar to that of Example 2, but instead of 0.05 wt. 0.5 parts by weight of MEK-1 are added. After thorough mixing, the material is separated by continuous centrifugation into individual phases. The organic phase is fed to a heating oil.

Example 7

The procedure is similar to Interleave 2, but instead of 0.05 wt. 0.4 parts by weight of MEK-1 are added. parts and in addition 0.1 wt. part of the distillation residue from acetic acid recovery from vinyl acetate production, containing

78.1% acetic acid, 8.1% acetic anhydride, 11.1% ethylidenediacetate, 0.2% vinyl acetate and resin admixture. After thorough mixing, the modified ivory material is separated by continuous centrifugation into individual phases.

Claims (4)

256170 10 of the modified slope material was allowed to sediment. Two layers were formed, while the bottom-aqueous layer was drained of the chemical water drains and the upper was removed and filtered by mechanical impurities instead of the heavy boiling oil. Example 5 A procedure similar to Example 4 was followed, only 0.2 wt.% Of MEK-1 was used. portions of formic, acetic and propionic acids in the form of an aqueous solution - scrubbing acidic water from cyclohexanone (acid scrubbing water from DS-104mali composition: formic acid = 3.8%, acetic acid = 1.5%) propionic acid = 1.6 wt%, cyclohexane = 0.1 wt%, cyclohexanol = 1.15 wt%, water = 92.4 wt%. The proportion of the top organic layer compared to Example 4 was 14% lower. Upon removal of the mechanical impurities by filtration, the top layer was used as a heating oil. EXAMPLE 6 The procedure is similar to Example 2, instead of 0.05 wt. parts of MEK-1 are added with 0.5 wt. After thorough mixing, the material is separated by continuous centrifugation into individual phases. The organic phase is saved in fuel oil. EXAMPLE 7 A procedure similar to Example 2 was followed, instead of 0.05 wt. parts of MEK-1 are added with 0.4 wt. parts and increased by 0.1 wt. part of a distillation residue from the recovery of acetic acid from a vinyl acetate plant containing 78.1% acetic acid, 8.1% acetic anhydride, 11.1% ethylidene diacetate, 0.2% vinyl acetate and resin admixture. After complete mixing, the modified sloping material is separated by continuous centrifugation into individual phases. SUBJECT · ......... A method for treating ivory materials, particularly hard-to-break trace emulsions from refinery and petrochemical processing of crude oil containing 3 to 75% by weight. % of water, with a mechanical impurities content of 0.1 to 25% by weight, characterized in that it is 1 wt. a portion of the slurry material is added to a total of 0.02 to 2 wt. parts of the by-product from the catalytic oxidation of cyclohexane to cyclohexanol and / or cyclohexanone, the isolated "hydrolysing" step as a distillation residue after separation of a substantial portion of the acid number of 100 to 350 mg KOH / g, 250 to 500 mg KOH / g; OH and bromine numbers of 5 to 35 g Br / 100 g and / or by-product of organochemical production containing at least one carboxylic acid C 1 to C 1 and the modified slope material is separated by centrifugation and / or settling. 2. A process for the processing of sloping materials according to claim 1, characterized in that the by-product of the organochemical production containing at least one carboxylic acid forms a distillation residue from the regeneration of acetic acid or rectification of the production of vinyl acetate containing 60 to 100% acetic acid mixture, acetic anhydride and ethylidene diacetate and / or a mixture of Cb to Cj acids in the scrubbing waters of cyclohexanone and / or cyclohexanol. 3. A process for processing slope materials according to claim 1 or 2, characterized in that the damp material, if any, is present at least in part prior to the addition of by-products and / or separation of a substantial part of the water by filtration and / or sedimentation and / or centrifugation. 4. A process for processing slope materials according to claim 1, characterized in that, after the separation of the sloping material, the layer formed by the water is drained into the chemically contaminated waste water, and the organic or predominantly organic layer is combusted directly or mixed with the fuming of the oil. and / or lead to the primary processing of the oil.