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Hydrocracking

The hydrocracking process has been known relatively recently, only since the mid-sixties of the last century. Although it should be noted that the practical application was established only by the mid-seventies in the United States of America.

Hydrocracking— hydrocatalytic processing of raw materials to obtain base oils with a high viscosity index (100 and above), low content of sulfur and aromatic hydrocarbons. Oils of the required quality are obtained not by removing undesirable components from raw materials (as is the case with selective solvent refining, adsorption refining and hydrotreating), but by converting them into hydrocarbons of the required structure due to hydrogenation, cracking, isomerization and hydrogenolysis reactions (sulfur, nitrogen, oxygen are removed ), which affects the stability of the resulting oils. Hydrocracking produces high-quality bases for a wide range of commercial lubricating oils: hydraulic, transformer, motor, energy, industrial, etc. In terms of their physical and chemical properties, HA oils are superior to "classic" mineral oils.

Hydrocracking synthetics, semi-synthetics or mineral water?

Let's try to figure it out. It is more correct, after all, to classify HA oils as a special class of oils, although motor oil manufacturers, in order not to frighten motorists with complex and unusual terminology, and also using the fact that the American Petroleum Institute recognized hydrocracking oils as synthetic, write something like “ synthetic technologies" etc. Some manufacturers do not write on their packaging at all how the base is produced, but in essence, HA oils are an improved mineral water.

Semi-synthetic a is, by definition, a mixture of mineral and synthetic base oils. The synthetic base is usually poly-alpha-olefins (PAO) or esters, or a mixture of them. In HA oils - mineral oil is replaced with cracked. The mineral base is the cheapest. This is a product of direct distillation of oil, consisting of molecules of different lengths (the length of hydrocarbon chains is 20 ... 35 atoms) and different structures.

Because of this heterogeneity:

• instability of viscosity-temperature properties
• high volatility
• low resistance to oxidation.

Mineral base- the most common motor oil in the world. PAO - the basis, these are hydrocarbons with a chain length of about 10 ... 12 atoms. It is obtained by polymerization (connection) of short hydrocarbon chains - monomers of 3 ... 5 atoms. The raw materials for this are usually gasoline molecules, or petroleum gases - butylene and ethylene. Advantages of PAO: do not freeze up to -60C, high resistance to temperature extremes, aging, low volatility. Such an oil base is 4.5 times more expensive than a mineral one. Esters are esters - products of neutralization of carboxylic acids with alcohols. Raw materials for production are vegetable oils, such as rapeseed, or even coconut. Esters have a number of advantages over all other known bases. Firstly, ester molecules are polar, that is, the electric charge is distributed in them in such a way that the molecule itself “sticks” to the metal. Secondly, the viscosity of esters can be set at the base production stage: the heavier alcohols are used, the greater the viscosity.

The disadvantages of traditional synthetic components are not limited to the high price. The fact is that both PAO and esters, additives dissolve in them worse, without which the production of modern motor oil is impossible. As for esters, they are distinguished by increased sensitivity to the ingress of water and, especially, water vapor. A very successful attempt to combine the high quality of synthetics with the non-aggressiveness of "mineral water" and, most importantly, at an affordable price, was the technology of hydrocracking, or "HC-synthesis".

Raw material for HA oils, unlike PAO, in not short hydrocarbon molecules protrude- monomers, but heavy, long hydrocarbon chains of 20 ... 35 atoms or more. Long chains break (cracking) into shorter "oily" ones with a homogeneous structure, break points in new shortened molecules saturated with hydrogen(hydrogenation). Hence the name - "hydrocracking". As a result of hydrocracking, a base oil with very high viscosity-temperature characteristics is obtained - the viscosity index (VI) reaches 130-150 units. For comparison, the VI of the best mineral bases is no more than 100. In addition, HC-oils do not corrode seals, are less “afraid” of water ingress, and are much better compatible with additives than PAOs and esters. And the most important thing! The hydrocracking base costs only 2 times more than the mineral base, i.e. 2.5 times cheaper than PAO and 3-5 times cheaper than esters. Therefore, the hydrocracking base has become widely used in the production of synthetics and semi-synthetics. it is better than mineral and cheaper than PAO.

Also, not so long ago, another interesting technology appeared: Shell GTL Pure Plus, in other words, it is the synthesis of the molecules we need with the properties we need from natural gas. It has little to do with the production of "conventional oils" and it is this that, today, can be called fully synthetic.

The fact is that GTL oils have all the advantages of PAO and, at the same time, do not have their disadvantages, including prices. And, accordingly, their performance is higher than that of hydrocracked oils, at least because they do not make semi-synthetics and do not add a mineral base. As for the price, it is at the level of "synthetic hydrocracking" oils from other well-known manufacturers, and the benefits are obvious.

I want to note that in the Shell line there are, and stand separately (HX8 and HX7), synthetic and semi-synthetic oils based on hydrocracking, produced using XHVI technology. And it is this technology that makes it possible to make HA oils with an ultra-high viscosity index, unlike other manufacturers of HA oils.

Many people wonder when they see hydrocracking oil on the shelves - what kind of car oil is it and what type should it be classified as: synthetic, semi-synthetic or mineral? In fact, hydrocracking oil is not semi-synthetic, but a separate type that does not belong to any of the above.

The developers managed to create something in between, and the result was a composition better than mineral oil, but slightly inferior to synthetic. It is impossible to ignore such a fact as cost. Due to the cheapness of the technology, hydrocracked oils are cheaper than synthetic oils.

Hydrocracking is a modern technology that allows you to refine and significantly improve the properties of the mineral base to the characteristics of synthetic oil. Oil is used for manufacturing, as it happens with mineral water, after which a number of chemical processes are performed that completely change the molecular structure of the composition. As a result, almost nothing remains of the starting characteristics inherent in mineral oil.

Thorough refining is needed to reduce the amount of impurities that are contained in the original composition of the oil. The output is an oil component that does not fit into any of the usual categories of motor oils - it is based on fewer extraneous “ingredients” than in mineral water, but it does not even reach synthetics in quality.

In practice, it looks like this: the mineral goes through several stages of cleaning excess impurities:

1. Dewaxing is a cleaning that minimizes the amount of paraffins - they increase the pour point of motor oils. Of course, it is impossible to remove all unnecessary impurities by this method, and the properties of mineral water deteriorate because of this.
2. Hydrotreating - being saturated with hydrogen, hydrocarbons change their structure (hydrogenation), and as a result, this process helps to increase the oxidation resistance of the oil.
3. Hydrocracking - during processing, several reactions occur, as a result of which sulfur and nitrogen compounds are removed, rings are split, bonds are saturated, paraffin chains are broken (cracking).

Compared to synthesis (the method of producing synthetic oil), the production of hydrocracked motor oils is less expensive, which positively affects the initial price of the product.

Hydrocracking Oil Properties

No matter how attractive everything may sound about deep cleaning, but after it the oil composition loses some of the protective properties that are so necessary for the engine. Undoubtedly, hydrocracking cleans everything and everyone, and all the necessary substances are subsequently created with the help of additives.

But the same cleaned resins, various kinds of acids enhance the stickiness properties of the oil film, improving its lubricating qualities. Sulfur/nitrogen compounds "withdrawn" from the composition during hydrocracking have antioxidant properties. Accordingly, some of the positive characteristics are safely reduced to zero.

Subsequently, when using a pure hydrocracked oil, you can find a high level of carbon deposits and less resistance to corrosion (when compared with synthetic). Of course, all this is replenished with additives, and as a result, when compared with the same synthetics, hydrocracked oils benefit from increased viscosity and oxidation resistance.

The production process and the components of hydrocracking oil themselves cannot be classified as expensive, respectively, the first and significant plus is an affordable price with very good quality. In addition, there are a number of other advantages:

• Minimization of friction level;
• Even with prolonged use, resistance to deposits and oxidation is observed;
• Excellent viscosity;
• Excellent interaction with additives;
• Minimal impact on elastomers.

Of the minuses, it is worth noting that hydrocracking motor oil:

• Predisposed to rapid evaporation;
• It loses useful qualities faster and requires replacement earlier than synthetics;
• Not designed for harsh environments.

But despite the fact that it costs much less than synthetic, you can put up with the shortcomings.

Very often recently, the concept of hydrocracking is closely associated with motor oils. Is this really an innovative technology or a clever ploy of car oil manufacturers? What is hydrocracking and what it is eaten with - in this article.

Hydrocracking is...

Hydrocracking is a catalytic biochemical process that has recently been used in oil refineries. High-boiling hydrocarbons convert crude oil into various types of more valuable products - kerosene, gasoline, diesel and jet fuel. The process itself takes place under hydrogen-enriched conditions, in the presence of catalysts, at a temperature of 250 to 425 °C and a pressure of 5 to 30 mega Pascals. Appropriate catalysts are selected, it is they that affect the high final yield of the main base component of oils with anti-oxidation resistance and a high viscosity index that are already inherent in them. The correct parameters of the technological regime allow almost completely removing harmful nitrogen, sulfur and other compounds at the molecular level. They form gaseous hydrogen sulfide with ammonia, which is easy to remove from the mixture. There are changes in the formulas of organomineral compositions: polycyclic aromatic compounds are hydrogenated, naphthenic rings and paraffin chain compounds decompose, and products are isomerized. To put it simply, it is simply a modification of a mineral base oil, which makes it possible to obtain a base oil that is similar in properties and quality to the most modern base synthetic oil. Paraffin hydrocarbons are the main composition of hydrocracking oils.

Synthetic or hydrocracked?

The main advantage of synthetic oils is thermal and oxidative stability. This property minimizes the creation and accumulation of soot and varnish. Lacquer in our case is a transparent, fairly strong film, which practically cannot be dissolved. They consist of oxidation products and settle on hot surfaces.
Also, the advantages of synthetics are minimal volatility and waste losses. These advantages reduce mechanical losses and wear of engine parts. Of course, it is worth noting that the operational life of synthetic oil exceeds mineral oil by 5 times. But the price of synthetic oil is 4-5 times higher than mineral oil. Of course, semi-synthetics used to be the middle option.
An alternative now is a highly refined mineral base oil, hydrocracked oil. Recent scientific and technological developments have made it possible to obtain base oils from petroleum, the viscosity, structure and properties of which are not inferior to those of polyalphaolefins (PAO). These alpha-olefin fractions are most commonly used in synthetic base oils. The process of hydrocracking at cost is much simpler and cheaper than the production of synthetic oil. That is why hydrocracking oils of the highest quality are relatively inexpensive.

Underwater rocks

Everyone knows that oils are synthetic, semi-synthetic and mineral. Well, what kind of hydrocracking oils? The price is like that of "mineral water", and the quality, according to the manufacturer, is like that of synthetics. What's the catch? After all, if everything were that way, it would become unprofitable to produce synthetic oils.
Synthetic oils are a product of gas synthesis, mineral oils are a product of oil distillation, semi-synthetics are a mixture of them in different proportions. The method of obtaining hydrocracking oil is identical to the mineral base at the first stages of production, then the oils undergo a deeper and more thorough purification using hydrocracking.

Hydrocracking technology

Oil, and this is a mixture of hydrocarbons, is sent for atmospheric distillation, resulting in fuel oil, which undergoes vacuum distillation for the finest division of hydrocarbon chains and rings. The heaviest fractions with a vacuum residue after this stage of processing are suitable for the production of base motor and gear oils with high viscosity. Lighter oils are the basis for the production of light industrial and transformer oils. Of course, a lot of impurities remain in oil, vacuum distillation does not end there. The additional cleaning process begins. The main impurities are sulfur, solid paraffins, organic acids, resins, polycyclic compounds, unsaturated hydrocarbons. These impurities cause corrosion, varnishes and soot, increase the pour point. This is why refining base oils is so important in production.

Cleanliness is the key to engine health

Impurities are removed from mineral oil by physicochemical methods, dewaxing prevents the liquid from solidifying, but it is almost impossible to completely get rid of impurities by such methods. Unsaturated hydrocarbons accelerate oil aging, but it is hydrotreating that helps get rid of them. Hydrocracking is an even more advanced purification method - several different reactions occur simultaneously. Molecular compounds in the form of rings and chains of different lengths are split into shorter ones, intermolecular bonds are saturated, and this is exactly what is needed for an oil with an ideal structure. In general, oils are hydrocarbons with a certain number of atoms. Carbon atoms can join in the form of a chain, long or short, or branch. The ideal structure for butter is precisely the straight chain. With this form of compounds, the oil will have the best properties and characteristics. It is during catalytic hydrocracking that the chains are straightened and rearranged. This process is called isomerization. Synthetic oil is obtained from gases, so the chain length is increased during the production of synthetic oil.

Summing up

Catalytic hydrocracking “discards” everything superfluous and the properties of oils are regulated by additives. Certainly. This process is not ideal, some impurities may remain in minimal quantities, because it is very difficult to filter out absolutely all impurities. Therefore, the appearance of a small amount of soot is quite possible. But high viscosity index, anti-oxidation properties, resistance to shear deformation and, especially, wear protection - in some cases even prevails over synthetic oils. On the other hand, synthetics have more homogeneous hydrocarbon compounds, this advantage is especially important in winter. The degree of perfection of hydrocracking and synthesis can be constantly increased.
I noticed that some companies classify hydrocracked oils as mineral oils, while others classify them as synthetic or semi-synthetic.
Still, price-quality is one of the main criteria for selecting oil, after recommendations and tolerances. The price of hydrocracking oil pleases, but synthetics are synthetics. The choice is yours.

Hydrocracking is designed to produce low-sulfur fuel distillates from various raw materials.

Hydrocracking is a later generation process than catalytic cracking and catalytic reforming, so it performs the same tasks as these 2 processes more efficiently.

Hydrocracking plants use vacuum and atmospheric gas oils, thermal and catalytic cracking gas oils, deasphalting oil, fuel oil, and tars as raw materials.

Technological installation of hydrocracking usually consists of 2 blocks:

Reaction block, including 1 or 2 reactors,

Fractionation unit consisting of a different number of distillation columns.

Hydrocracking products are motor gasolines, jet and diesel fuel, feedstock for petrochemical synthesis and LPG (from gasoline fractions).

Hydrocracking increases the yield of gasoline components, usually by converting a feedstock such as gas oil.

The quality of the gasoline components that this achieves is not achievable by re-passing the gas oil through the cracking process in which it was obtained.

Hydrocracking also makes it possible to convert heavy gas oil into light distillates (jet and diesel fuel). During hydrocracking, no heavy non-distilling residue (coke, pitch or VAT residue) is formed, but only lightly boiling fractions.

Benefits of hydrocracking

The presence of a hydrocracking unit allows the refinery to switch its capacity from the production of large quantities of gasoline (when the hydrocracking unit is operating) to the production of large quantities of diesel fuel (when it is turned off).

Hydrocracking improves the quality of gasoline and distillate components.

The hydrocracking process uses the worst of the distillate components and produces an above average quality gasoline component.

The hydrocracking process produces significant amounts of isobutane, which is useful for controlling the amount of feedstock in the alkylation process.

The use of hydrocracking units gives an increase in the volume of products by 25%.

About 10 different types of hydrocracking units are currently in common use, but they are all very similar to the typical design.

Hydrocracking catalysts are less expensive than catalytic cracking catalysts.

Technological process

The word hydrocracking stands for very simply. This is catalytic cracking in the presence of hydrogen.

The introduction of cold hydrogen-containing gas into the zones between the layers of the catalyst makes it possible to equalize the temperature of the feed mixture along the height of the reactor.

The movement of the raw mixture in the reactors is descending.

The combination of hydrogen, catalyst and the appropriate process conditions allow cracking of low quality light gas oil, which is produced in other crackers and is sometimes used as a component of diesel fuel.
The hydrocracking unit produces high quality gasoline.

Hydrocracking catalysts are usually sulfur compounds with cobalt, molybdenum or nickel (CoS, MoS 2 , NiS) and aluminum oxide.
Unlike catalytic cracking, but just like catalytic reforming, the catalyst is arranged in a fixed bed. Like catalytic reforming, hydrocracking is most often carried out in 2 reactors.

The raw material supplied by the pump is mixed with fresh hydrogen-containing gas and circulating gas, which are injected by the compressor.

The feed gas mixture, passing through the heat exchanger and furnace coils, is heated to a reaction temperature of 290-400°C (550-750°F) and is introduced into the reactor from above under a pressure of 1200-2000 psi (84-140 atm). Given the large heat release during hydrocracking, cold hydrogen-containing (circulation) gas is introduced into the reactor in the zones between the catalyst layers in order to equalize temperatures along the height of the reactor. During passage through the catalyst bed, approximately 40-50% of the feed is cracked into products that have gasoline boiling points (boiling point up to 200°C (400°F).

The catalyst and hydrogen complement each other in several aspects. First, the catalyst is cracked. In order for cracking to continue, a heat supply is required, that is, it is an endothermic process. At the same time, hydrogen reacts with molecules that are formed during cracking, saturating them, and in this case, heat is released. In other words, this reaction, which is called hydrogenation, is exothermic. Thus, hydrogen provides the heat necessary for cracking to proceed.

The second is the formation of isoparaffins. Cracking produces olefins that can combine with each other, leading to normal paraffins. Hydrogenation quickly saturates the double bonds, often producing isoparaffins, and thus preventing the re-production of unwanted molecules (the octane numbers of isoparaffins are higher than with normal paraffins).

The mixture of reaction products and circulating gas leaving the reactor is cooled in a heat exchanger and cooler and enters the high pressure separator. Here, the hydrogen-containing gas is separated from the liquid for the reverse direction into the process and mixing with the raw material, which from the bottom of the separator through the pressure reducing valve enters further into the low-pressure separator. Part of the hydrocarbon gases is released in the separator, and the liquid stream is sent to a heat exchanger located before the intermediate distillation column for further distillation. In the column, at a slight overpressure, hydrocarbon gases and light gasoline are released. The kerosene fraction can be isolated as a side cut or left with the gas oil as a distillation residue.

Gasoline is partially returned to the intermediate distillation column in the form of acute irrigation, and its balance amount is pumped out of the plant through the “alkalinization” system. The residue from the intermediate distillation column is separated in the atmospheric column into heavy gasoline, diesel fuel and a fraction >360°C. Since the feedstock at this operation has already undergone hydrogenation, cracking and reforming in the 1st reactor, the process in the 2nd reactor is in a more severe mode (higher temperatures and pressures). Like the products of the 1st stage, the mixture leaving the 2nd reactor is separated from hydrogen and sent for fractionation.

The wall thickness of the steel reactor for a process running at 2000 psi (140 atm) and 400 ° C sometimes reaches 1 cm.

The main task is to prevent cracking from getting out of control. Since the overall process is endothermic, a rapid rise in temperature and a dangerous increase in the cracking rate are possible. To avoid this, most hydrocracking units contain built-in devices to quickly stop the reaction.

The gasoline of the atmospheric column is mixed with the gasoline of the intermediate column and removed from the installation. Diesel fuel after the stripping column is cooled, "alkaline" and pumped out of the unit. The >360°C fraction is used as a hot stream at the bottom of the atmospheric column, and the rest (residue) is removed from the plant. In the case of the production of oil fractions, the fractionation unit also has a vacuum column.

Catalyst regeneration is carried out with a mixture of air and inert gas; the service life of the catalyst is 4-7 months.

Products and outputs.

The combination of cracking and hydrogenation produces products whose relative density is much lower than that of the feedstock.

Below is a typical distribution of yields of hydro-cracking products using gas oil from a coker and light fractions from a catalytic cracker as a feedstock.

Hydrocracking products are the 2 main fractions that are used as gasoline components.

Volume fractions

Coking gas oil 0.60

Light fractions from the catalytic cracking unit 0.40

Products:

Isobutane 0.02

N-Butane 0.08

Light hydrocracking product 0.21

Heavy hydrocracking product 0.73

Kerosene fractions 0.17

Recall that from 1 unit of raw materials, about 1.25 units of products are obtained.

It does not specify the required amount of hydrogen, which is measured in standard ft 3 /bbl feed.

The usual expense is 2500 st.

The heavy product of hydrocracking is naphtha (naphtha) containing many aromatic precursors (i.e., compounds that readily convert to aromatics).

This product is often sent to a reformer for upgrading.

Kerosene cuts are a good jet fuel or distillate (diesel) fuel feedstock because they contain little aromatics (due to saturation of the double bonds with hydrogen).

Residue hydrocracking.

There are several models of hydrocracking units that have been designed specifically for the processing of residues or residues from vacuum distillation.

The output is more than 90% of the residual (boiler) fuel.

The objective of this process is to remove sulfur as a result of the catalytic reaction of sulfur-containing compounds with hydrogen to form hydrogen sulfide.

Thus, a residue with a sulfur content of not more than 4% can be converted into a heavy fuel oil containing less than 0.3% sulfur.
It is necessary to use hydrocracking units in the general scheme of oil refining.

On the one hand, the hydrocracking unit is the centerpiece, as it helps balance the amount of gasoline, diesel and jet fuel.
On the other hand, feed rates and operating modes of catalytic cracking and coking units are equally important.
In addition, alkylation and reforming should also be considered when planning the distribution of hydrocracked products.