VACUUM DISTILLATION RESIDUES

Properly speaking, steam cracking is not a refining process. A key petrochemical process, it has the purpose of producing ethylene, propylene, butadiene, butenes and aromatics (BTX) mainly from light fractions of crude oil (LPG, naphthas), but also from heavy fractions hydrotreated or not (paraffinic vacuum distillates, residue from hydrocracking HOC). 

The tendency towards explosive decomposition noted for dihalo-2,4-hexadiyne derivatives appears to be associated more with the co-existence of halo- and acetylene functions in the same molecule, than with its being a polyacetylene. Haloacetylenes should be used with exceptional precautions [1], Explosions may occur during distillation of bromoacetylenes when bath temperatures are too high, or if air is admitted to a hot vacuum-distillation residue [2], Precautions necessary in isolating and handling such compounds on the small (1 g) scale are detailed [3], Individually indexed compounds are ... 

Vacuum distillation residues, 408 Vacuum ovens, 408 Vacuum pumps, 409 Vanadocenes, 409 Vapour cloud explosions, 409 Vapour explosions, 410 Vegetable oils, 411 Vent lines, 411 Vinylmercury hydrides, 411 Vinylsiloxanes, 411... 

There are analogies between the characterization of crude distillation residues and the previous feeds. The main difference is that for atmospheric and vacuum distillation residues of crude PINA and H/C can be estimated only through the kind of analysis (such as NMR) not normally available in refineries. Moreover, their final boiling point is not defined and the internal distribution of the different hydrocarbon classes of alkanes, cyc/o-alkanes and aromatics has to be deduced in a different way. Inside each macro-class, the relative amount of the components can be derived from the following statistical distribution ... 

Figure 1.13 Processing of plastic wastes in refinery units.19 VVA pre-treated mixed plastic scrap AR residue from the atmospheric distillation process VR vacuum distillation residue VisR visbreaker residue VVR vacuum visbreaker residue.

Recycling spent caustic downstream from the desalter can be only a limited solution. This is because of the detrimental aikalinization of the crude (creation of emulsions), or if vacuum distillation residues are ro serve as feed for visbrealcing (standard 3 ppm of Na in the feed or 8 in the crude). It can be contemplated only in simple refineries, but not in the complex ones that produce considerable amounts of spent caustic. 

Mass spectrometry allows analysis by hydrocarbon family for a variety of petroleum cuts as deep as vacuum distillates since we have seen that the molecules must be vaporized. The study of vacuum residues can be conducted by a method of direct introduction which we will address only briefly because the quantitative aspects are ek r metiy difficult to master. Table 3.6 gives some examples the matrices used differ according to the distillation cut and the chemical content such as the presence or absence of olefins or sulfur. 

SARA (Saturates, Aromatics, Resins, Asphaltenes) analysis is widely practiced on heavy fractions such as vacuum and atmospheric residues and vacuum distillates for two purposes ... 

Feedstock Paraffinic crude Naphthenic crude Vacuum distillate Vacuum residue Deasphalted atmospheric residue... 

In the 1970 s, heavy fuel came mainly from atmospheric distillation residue. Nowadays a very large proportion of this product is vacuum distilled and the distillate obtained is fed to conversion units such as catalytic cracking, visbreaking and cokers. These produce lighter products —gas and gasoline— but also very heavy components, that are viscous and have high contaminant levels, that are subsequently incorporated in the fuels. 

The distillation of crudes chosen for their yield in heavy fractions is the most common means. Bitumen is extracted from the residue from a vacuum distillation column (a few dozen mm of mercury), the latter being fed by atmospheric distillation residue. Unlike the practice of a decade ago, it is now possible to obtain all categories of bitumen, including the hard grades. 

Vacuum distillation of the atmospheric residue complements primary distillation, enabli r.ecoyery of heavy distillate cuts from atmospheric residue that will un r o further conversion or will serve as lube oil bases. The vacuum residue containing most of the crude contaminants (metals, salts, sediments, sulfur, nitrogen, asphaltenes, Conradson carbon, etc.) is used in asphalt manufacture, for heavy fuel-oil, or for feed for others conversion processes. 

Feedstocks for this very flexible process are usually vacuum distillates, deasphalted oils, residues (hydrotreated or not), as well as by-products from other processes such as extracts, paraffinic slack waxes, distillates from visbreaking and coking, residues from hydrocracking, converted in mixtures with the main feedstock. 

Figure 10.7 presents the case of an FCC feedstock comprising a mixture of vacuum distillate and light atmospheric residue, and the case of an FCC feedstock composed of vacuum distillate and DAO, as well as the constraints of such configurations. 

Figure 10.8 presents a variant of the FCC process, the RCC (Residue Catalytic Cracking) capable of processing heavier feedstocks (atmospheric residue or a mixture of atmospheric residue and vacuum distillate) provided that certain restrictions be taken into account (Heinrich et al., 1993). 

Feedstocks are light vacuum distillates and/or heavy ends from crude distillation or heavy vacuum distillates from other conversion processes visbreaking, coking, hydroconversion of atmospheric and vacuum residues, as well as deasphalted oils. 

The conversion products, other than gas and hydrogen sulfide (H2S), are essentially a gasoline fraction that, after pretreatment, will be converted by catalytic reforming an average quality distillate fraction to be sent to the gas oil pool and an atmospheric residue or vacuum distillate and vacuum residue whose properties and impurity levels (S, N, Conr. 

Vacuum residue case Gasoline Gas oil Atm. residue Vacuum distillate Vacuum residue... 

Mix 50 ml. of formalin, containing about 37 per cent, of formaldehyde, with 40 ml. of concentrated ammonia solution (sp. gr. 0- 88) in a 200 ml. round-bottomed flask. Insert a two-holed cork or rubber stopper carrying a capillary tube drawn out at the lower end (as for vacuum distillation) and reaching almost to the bottom of the flask, and also a short outlet tube connected through a filter flask to a water pump. Evaporate the contents of the flask as far as possible on a water bath under reduced pressure. Add a further 40 ml. of concentrated ammonia solution and repeat the evaporation. Attach a reflux condenser to the flask, add sufficient absolute ethyl alcohol (about 100 ml.) in small portions to dissolve most of the residue, heat under reflux for a few minutes and filter the hot alcoholic extract, preferably through a hot water fuimel (all flames in the vicinity must be extinguished). When cold, filter the hexamine, wash it with a little absolute alcohol, and dry in the air. The yield is 10 g. Treat the filtrate with an equal volume of dry ether and cool in ice. A fiulher 2 g. of hexamine is obtained. 

This is a way to do this procedure without having to use one of those crazy tube furnaces stuffed with thorium oxide or manganous oxide catalyst [21]. The key here is to use an excess of acetic anhydride. Using even more than the amount specified will insure that the reaction proceeds in the right direction and the bad side reaction formation of dibenzylketone will be minimalized (don t ask). 18g piperonylic acid or 13.6g phenylacetic acid, 50mL acetic anhydride and 50mU pyridine are refluxed for 6 hours and the solvent removed by vacuum distillation. The remaining residue is taken up in benzene or ether, washed with 10% NaOH solution (discard the water layer), and vacuum distilled to get 8g P2P (56%). 

The combined organic solutions were washed five times with saturated sodium chloride solution and subsequently dried Over magnesium sulfate. After concentration of the extract in a water-pump vacuum the residue was distilled through... 

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