JPS62179592A - Cracking of dispersed catalyst using methanol as co-reactant - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a method for fluid catalytic cracking of a mixture of hydrocarbon oils and methanol in the presence of a zeolite fine particle dispersion exemplified by ZSM-5. .

[Prior Art] The use of zeolite catalysts mainly consisting of zeolite Uke is being accepted. Most known or proposed operations involving zeolite-catalyzed hydrocarbon reactions (such as in fixed bed reactors with particles of diameter 2+1111 or larger or from 1 to 140 as in fluid catalytic cracking (FCC) operations) micron,
It utilizes a fluidized bed of catalyst with an average particle size of about 60 microns. In all of these operations, the reaction is carried out by contacting a relatively large amount of catalyst with the charge for a given period of time.

U.S. Pat. No. 3,951,781-HJ teaches mixing hydrogen donors (e.g., CH, 0H1C2HsOH, ethers, etc.) with deasphalted residue, followed by fluid catalytic cracking. are doing. methanol//
The ratio of hydrocarbon charges is 0.0 on a stoichiometric basis.
01/1 to 5/1, preferably 0. . 05/1~0.30
/1, but the ratio is based on the amount of hydrogen deficient in the raffinate obtained from solvent deasphalting of the vacuum distillation column residual oil, the amount of sulfur, nitrogen and oxygen in the raffinate, the amount of polycyclic aromatics, and the amount of polycyclic aromatics used. The composition of the catalyst used can be varied as a function of the desired conversion level. It is important that it is preferable to avoid a fairly moderate amount of methanol in the feedstock since methanol tends to react with itself under the same conditions.

U.S. Pat. No. 3,974,063 discloses the nitrogen-containing oil stock, such as shale oil synthetic crude oil, by cracking it with an acidic zeolite cracking catalyst in the presence of 02-C1 hydrocarbons and/or methanol. A method for converting contained oil stocks is taught. Co-cracking of high nitrogen content stocks with carbon-hydrogen contributors provides acceptable denitrification of the charge, thereby reducing the need for subsequent hydrotreating. ~593℃ (below 900-1100)
2-15 wt.% faujasite and/or dispersed in the mother (4) at a temperature of
or promoted by a mixture of large and small pore zeolites using mordenite zeolite.

The pressure is typically below 800 kPa (100 psig). The methanol/hydrocarbon ratio in the charge is on a stoichiometric basis from 0.01/1 to 5/1, preferably 0.05.
/1 to 0.30/1.

U.S. Pat. No. 4,002,557 teaches that an H2-rich material, H2 donor or 82 generating material, such as methanol, is mixed with gas oil, then preheated, mixed with a catalyst, and FCC
It states that the reaction is carried out in an apparatus.

It is preferable to avoid feeding a significant excess of methanol in the charge, since methanol itself tends to react with each other under the same conditions.

U.S. Pat. No. 4,263,126 discloses a method for converting waxy or viscous hydrocarbon oils to lower the pour point or to provide less viscous coal and arsenic oils. It is aimed at

1-IZSM-5,823M-11,823M-
Zeolite neck resized dispersions such as 12, II Z SM-23, 823M-35 and 823M-38 are used as ultrafine particles with particle sizes from less than 0.01 microns to 5 microns. It is preferred to use powder f during formation. This is convenient when separation or reuse of the powder is not required and is the cheapest. re f
The active dispersion is heated to 200 DEG to 500 DEG C. for a period of time effective to induce conversion, usually 0.1 to 72 hours.

U.S. Pat. No. 4,328,834 discloses methanol,
teaches a method for the conversion in the presence of a special type of zeolite catalyst maintained in upward flow conditions for oxygen-containing carbonization mixtures such as lower alcohols and ethers, aldehydes and ketones. , in which a charge is discharged from a dispersed catalyst phase riser contacting zone into a denser upwardly flowing fluidized mass of catalyst particles. The riser residence time is 1-10 seconds and the residence time in the denser phase is 5-80 seconds. The density of the catalyst in the riser is 0.016 to 0,24 g/ec (1 to 15 bonds/cubic foot), and the catalyst density in the denser phase is 0.
．． 32-0.64 g/cc (20-40 bonds/cubic foot). Heat exchange 2': r is the riser temperature 10
The temperature of the dense fluidized bed was increased to 427°C (below 195°C).
(below 800), preferably 407°C (below 765). At the bottom of the dense fluidized bed the reactor pressure is limited to 2-2.5 atmospheres. The catalyst is a silica, a zeolite with a high silica/'alumina molar ratio and high activity, even with a 'alumina molar ratio of 30 or more.

Activity is usually defined by the alpha value. α activity is determined by U.S. Patent No. 3,354,078 Specification 9 and
Tarisis J public of canal sis
Vol. 1, pp. 522-529 (August 1965).

Typically, ZSM-5 zeolites are activated by calcining them to remove water and organic deposits. Calcination can be carried out by heating the zeolite in an inert gas such as air, hydrogen, or nitrogen, thereby obtaining the desired activity.
The heat treatment is carried out for at least 1 hour,
The heat treatment can last from 1 to 24 hours. Although the heat treatment is performed in a dry state (containing no water), up to 3% by weight of steam can be included in the firing atmosphere.

Since catalytic cracking operations are endothermic, this makes them thermally self-cooling at relatively high reaction rates. The catalyst is regenerated by burning coke to create a maximum temperature of about 730° C. (below 1350° C.); the thermal catalyst is then recycled and mixed with the charged oil. The catalyst is preferably a zeolite mixed in a matrix, a relatively inert compound that acts as a heat sink to transfer heat from the regenerator to the cracker. Also, all amorphous catalysts can be used.

[Problem sought to be solved by the invention] Since the discovery of highly active zeolite cracking catalysts, the use of such catalysts without the accompaniment of many inert materials has been sought for many years as a major improvement in catalytic cracking operations. It's here. However, it has not been practical to use Zeolite 1-catalyst without accompanying materials without the use of a means of supplying heat to the reactor.

The opposite problem occurred in the case of the Fischer-Trobsch synthesis, the oxo process, and the highly exothermic reactions of the conversion of oxygen-containing compounds. Attempts have been made to balance the exothermic and endothermic reactions described above by transferring heat through heat exchangers, but there are no methods for achieving a more sensitive thermal equilibrium between exothermic and endothermic reactions. is necessary.

A method has now been discovered for modifying the cracking reaction by balancing the endothermic FCC cracking reaction with the exothermic reaction described above while minimizing the amount of coke formation.

[Means for Solving the Problems] Accordingly, the present invention provides a method for catalytic cracking of hydrocarbons without catalyst regeneration, in which hydrocarbons, oxygen-containing carbon compounds, and hydrocarbons are cracked in a reactor, and oxygen-containing contacting a finely divided and highly active zeolite catalyst capable of exothermically converting carbon compounds to hydrocarbons enriched in carbon, wherein at least a major share of the heat of reaction of the endothermic catalytic cracking reaction is the oxygen-containing carbon compound. The object of the present invention is to provide a method for catalytic cracking of hydrocarbons without catalyst regeneration, characterized in that the hydrocarbons are supplied through a ripening reaction to produce hydrocarbons.

[For FLMI] The closer the two reactions are, the smaller the amount of coke produced will be if the oxygen-containing carbon, for example, methanol is in a proper ratio of carbon to arsenic. As a result, the temperature equilibrium at the catalyst surface is affected more locally. Preferably, the methanol is mixed with the catalyst upstream of the cracker and then mixed with the hydrocarbon. This protects the catalyst from sorption of poisonous compounds (eg nitrogen-containing compounds) during the initial steps of the reaction, especially when methanol is insoluble in the non-polar hydrocarbon charge.

The catalyst is preferably a finely divided zeolite in the as-synthesized crystalline form with a very high acid activity, preferably 500 or more, optimally 1000 or more (e.g. α value = 1600), and the catalyst has a very high acid activity. It is preferable that the ratio of carbon to hydrocarbon is very small (approximately 0.02 parts carbon to one part arsenide, or a catalyst/hydrocarbon ratio of 0.01). Preferably, the catalyst particle size is 50 microns or less.

Balancing the heat absorption of the hydrocarbon oil with the heat generation of methanol requires a thermal balance based on the methanol/hydrocarbon oil weight ratio within the catalytic cracking device. The ff1ffi ratio of methanol/hydrocarbon oil is preferably in the range of 1/20 to 2/1. If the feedstock is charged at a temperature below the reaction temperature, more methanol is used. This is based on the fact that each gram of methanol converted releases 300 to 400 calories of heat and each gram of hydrocarbon oil that is cracked absorbs 100 to 170 calories of heat.

The above relationship allows the cracking reaction to be sustained virtually completely by the highly exothermic conversion of methanol in the presence of a low concentration of highly active zeolite catalyst, and the cracking reaction is prevented from being thermally cooled by the cracking reaction itself. Ru.

When a highly active zeolite catalyst with an activity or α value of about 1600 is used in a very finely divided state, such as an average particle size of 3 The contained compound is vaporized, and then at a temperature range of 450 to 650°C for 1 to 60 seconds,
Preferably, with a reaction period of 6 to 15 seconds, -! cracking said gas oil without adding 5 amounts of additional heat, without producing large amounts of coke or gas, and with increased production of low boiling range hydrocarbons and unsaturated hydrocarbons; , it was specifically observed that methanol was converted at the same time. The U of the catalyst can be up to 5.0% by weight of the hydrocarbon oil, preferably less than 1.0% by weight of the hydrocarbon oil, and optimally less than 0.02% by weight of the hydrocarbon oil. When the amount of catalyst is 0.02 ML%, the amount of catalyst consumed is almost the same as the normal loss during regeneration operation.
There is no need to regenerate the catalyst.

As shown in FIG. 1, the method of the present invention comprises a preheated hydrocarbon such as gas oil in conduit (12), a catalyst in conduit (14) and an oxygen-containing alpha compound such as methanol in conduit (13). are mixed to form a warm mixture in the FP tubes (21) and the resulting mixture is mixed with the recycled hydrocarbons in the conduits (4) in the conduits (23) entering the heater (25). Form a charge mixture. The charging raw material mixture is 500 to 65
heating to 0°C (below 932-1202), conduit (26);
The riser reactor (31) is charged via line (28) and line (29). The products, unreacted feedstock and catalyst are discharged via line (33) to a heat exchanger (35) to preheat the gas oil charged via line (11). The cooled riser effluent is passed through conduit (37) to the rectifier (4).
1) Charge I\. CO2 and CO are removed through conduit (43), C3-C6 product neck is taken out through conduit (45), C6-Cps product deposits and water are removed through conduit (47), and water reaction carbonization such as light oil is removed. Hydrogen is removed from the conduits (4). Guide'! '(47) The substance in the decanter (
51), the 06-CI5 products are discharged through conduit (53), and the water and catalyst are discharged through conduit (55) for disposal.

The riser reactor (31) is an otherwise conventional reactor that does not require a cyclone separator or catalyst stripping zone.

The charge in conduit (26) has been heated to approximately the reaction temperature and is then subjected to riser reaction? Enter Ko (31).

The temperature of the riser reactor (31) is controlled by balancing the oxygen-containing compound/hydrocarbon ratio in the feedstock mixture to the desired conversion level.

The riser reactor (31) is effective and automatic because the exothermic methanol conversion reaction is always 100% complete, but the endothermic hydrocarbon oil conversion is limited by the amount of heat released by methanol conversion. Equipped with built-in temperature control II mechanism.

If the charge has a high nitrogen content, a heater (25
) can separately heat the mixture of oxygen-containing compound and catalyst which enters the heater (25) via the conductor (17). A separately heated oxygen-containing compound/catalyst mixture is passed through a conduit (
27) to the conduit (26>) and passes through the conduit (28) and the conduits (2) to the riser reaction 3 (31). Conduit (21
>, conduit (23) and conduit (26) are heated as a moving mixture, and also for hydrocarbon conduit (21),
The F% tube (23) and the conduit (26) may be heated separately as the oxygen-containing compound is transferred through the conduit (17) and the conduit (27), and the catalyst is connected to the conduit from the conduit (14). to a conduit (28).

[Example] The present invention will be further explained with reference to an example (hereinafter, simply referred to as "one example" unless otherwise specified).

The cracking reaction is 0.02 to 1. om, 1-5 ZS
It was carried out in an isothermal overhead plug flow reactor using a jl-hexadecane charge containing M-5 powder. The average crystal size was 0.02.-0.05 microns. Catalyst particle size was less than 44 microns.

Tables 1 and 2 summarize the results of the hexadecane cracking experiments described above. The pure compound hexadecane should exhibit a first-order cracking rate that depends on the hydrocarbon concentration, regardless of whether cracking proceeds via carbonium-ions or free radical rates. 1n at three catalyst concentrations and two temperatures
(primary conversion rate) and liquid hourly space velocity -' (L II S
The plot of V-1) is shown in FIG. 2, which proves the first-order reaction rate described above. The activation energies derived from the above data are shown in FIG.

For hexadecane non-contact, the observed 5 0 , 1
The activation energies of 11 mol of kea and 11 mol of 46.5 kea are 50-60 k, which is often described for free radical cracking reactions of pure hydrocarbons.
It is very close to the ca11 mole range. Similarly, 2
For cracking experiments using a catalyst/oleaginization of It is included within the range of 15"-30 kcal 11 mole. The fact that the activation energies measured above are on the lower side of the activation energies stated above can be explained by the non-isothermal nature that occurs when the feedstock vaporizes and enters the reactor. Relatively low temperatures at the beginning of the reaction, when the catalyst is most active, will probably result in an artificially low conversion and therefore an artificially low activation energy, assuming isothermality is ensured. .

When the catalyst concentration was increased to a catalyst/hydrocarbon ratio of lXl0-2, the activation energy dropped to about 2.5 kcal. Although such a drop in activation energy suggests the initiation of a mass-transfer-limited reaction, the mathematical standard values found indicate that mass-transfer limitations (interphase and intracrystalline) are limited under the reaction conditions described above. It shows that it won't happen.

Simply put, the fruits $1-12 as described in Section 1k and analyzed in FIGS. The purpose of this study is to test a theoretical model that takes into consideration the necessary conditions for cracking with a finely dispersed catalyst. Due to its inherent activity, it is heat transfer limited.

The interesting finding is that when a small amount of highly active ZSM-5 (α value = 1600) with a low amount of ffi < about 0.02 ffi 5') is dispersed in the hydrocarbon stream charged to the riser reactor,
It is capable of producing significant levels of conversion. The plot depicted in Figure 4 shows that operation in a narrow tube produces a higher surface area/volume than operation in a wide tube, thereby providing better heat transfer from the heated outer wall of the reactor to the reaction. This is especially important because it indicates that the

The results from the pond show that about 50% of l-hexane was heated to 610°C (113°C).
0) and a gas residence time of 1.5 seconds or less and a small amount of about 0.02 weight of ZSM-5 catalyst is converted.

The intracrystal or (■) mass transfer limitation is under the above conditions a
It wasn't noticed. Another important result is that the endothermic hexadecane cracking reaction is high! When the concentration of ZSM-5B catalyst (α value = 1600> is increased to 1.0ffif1%, it becomes a heat transfer limited type. Fruit @1~1
Using a catalyst similar to that used in 2, we investigated the cracking behavior of hexadecane alone and methanol alone, providing information on the heat balance between the two reactions at one selected temperature and LH3V of 18.6. (Hexadecane '80)
? ,? /methanol 20%) was carried out to study the conversion behavior. These experiments were conducted in an open column tubular reactor impregnated with a heated isothermal fluidized sand bath. LH8V
is based on the heated empty volume of the reactor.

The data for runs 13-24 are summarized in Table 2, with detailed product analyzes of particular interest. Regarding LH9V, the above-mentioned experiments @13-24 are high L HS V experiments (Experiment 1.2
．． 5.6.9.10) and low L II S V experiment Q3.4.7.8.11.12). Fruit 91
3 and 1 do not use catalyst and are therefore similar to runs 9-12 in this respect. Fruit @15.18.2
1 and 24 for a charge mixture of 80% by weight rhohexadecane and 2% methanol. This is a thermal equilibrium experiment at a temperature of I. Higher temperature, 607℃<1
125 below) and 588°C (under 1090)
Nos. 15 and 18 show that the conversion of hexadecane to much lower boiling materials is excellent, but produces only a small amount of methane.

Additionally, the experiments described above with the hexadecane and methanol feed mixture indicate that all the methanol is at least converted to dimethyl ether (DME) and most of the DMIE is decomposed into methane and water, thereby liberating a large amount of water. is important.

Also, 607℃ (below 1125) and 588℃ (1090℃)
In experiments @15 and 18 below), it is observed that methane then combines to give more Fj,m products such as propene, and also more C6s and C6s. Also, in Experiment 15 at 607°C (below 1125), more importantly, C7 class, 06 class and C, I up to the neck
＼ also involves an addition reaction. In 28 experiments at low temperatures, Runs 21 and 24, C50 additions were made in WA with similar additions of propene exceeding methanol alone and hexadecane alone.

It is even more important that the actual @15 produces less than 2/3 of the water compared to the actual @16, which is probably due to the fact that <DME reacts to produce products other than methane and water. However, A@18 is lower in temperature than actual @15 and produces less water. However, this means that in Experiment 22 at 521°C, the amount of water produced was less, but at the same temperature. In fact @21, water production I is particularly different from most.

In addition, in the above experiments, the conversion rate of hexadecane was 90 weight 26 or more for the two experiments at the higher temperature, and the conversion rate of methanol was 1 o o for the three experiments at the higher temperature.
Indicates that it was qo.

The data in Table 2 is summarized in Figure 6, which is an Arrhenius plot for the cracking of hexadecane and hexadecane/methanol compounds. This figure shows that 20% by weight of methanol and 80% by weight of n-hexadecane are added to the hexadecane charging raw material, and then highly active Z SM
-5 catalyst (1ffi% of the total charge), the conversion level obtained when using hexadecane as a single charge and pure meta as a charge, /-
The lowest temperature at which the conversion of hexadecane increases above the level of conversion obtained when using a
In experiment 24 at 8 °C (below 900 °C), the methanol in the reaction product diluted the hexadecane, resulting in a hexadecane conversion below that achieved using pure hexadecane due to the slow reaction rate of methanol. decreases. That is, at higher temperatures, the high conversion of the hexadecane-methanol mixture is primarily due to the fact that the cracking reaction becomes reactor heat transfer limited.

Therefore, the exothermic methanol reaction makes the heat contribution to the hexadecane reaction fm possible in the entire reaction zone, thereby maintaining the reaction temperature at the selected level uniformly and not just along the heat transfer surface. be able to.

The third is the mechanical analysis value of the methanol/'hexadecane experiment. This table shows that as long as the addition of methanol to hexadecane increases the amount of heat released by the reaction of methanol to DME to paraffins + aromatics almost exactly equal to the heat absorbed in the now more widespread endothermic cracking reaction of hexadecane. Directs the hexadecane reaction to very high conversions.

c, jJ electric 2.8
3 4. :(52,78 CIlls
1.19 1.79
1.20C, JPO, 190,240,21 (J+JffO, 140,20 C+Jfl O,
1131,070,E15 (Class 314
0.19 1.13 0.15
1.15C+J1 0
．． 63 0.26 0.39
0.26 Hexadecane 8B, 11 33
．． 81 5.58 Substances with boiling points higher than 37.07 0.53 0.4:
Conversion rate of 1n-c+5lls<13.89
(+6.19 93.02 62.9
IIc (%) from 3MEO11
4,90 2.2GN1 mi011 conversion rate 100 5
4.03 Mixed 'l@': n C+g1(i+/M
l':0111■j combined ratio n-C+JI, <80i1j
M% and M+': 01H119202+
22 23 244.10
2.20 2.17
1.25 0.893.15
2.26 4.14
0.91 0.551.54
1.07 0.94
0.78 0.480.21
0,63 0,52 0
．． 56 0,430.21
0.41, G, 5
t O,3+1.13 0
．． 33 0,59 0.30
0.310.20 0.22
0.83 0.2θ
0.180.30 0.68
0.40 0.3Q 2. +
0゜6゜72 9B, 73 45.91
25.20 64.4[+5
8.630.7G O,691,
6291,'60 1.27 54.09
G9.50 35.54 2
G, 712.92 8
．． 52 5.7+3 2.631
00 100
17.50 49.20120j
l'jMj%.

The above-mentioned example uses ZSM to catalytically promote the exothermic conversion and endothermic catalytic cracking reaction of the acetate compound (ZSM).
5, but a pond zeolite or other acidic catalyst can be used to promote the above-mentioned reaction.

Large pore zeolites such as X-type zeola fl., Y-type zeolite, and mordenite can be used provided they have sufficient acid activity to promote cracking reactions and conversion of oxygen-containing compounds. Alumina, silica
Amorphous materials such as alumina, clay, etc. can also be used if they have the necessary acid activity. many places,
Acids can be made by contacting the amorphous material with other acidic compounds, for example by impregnating a relatively inert compound with a solution of a strongly soluble mineral acid, or by contacting alumina with a Friedel-Krach metal halide. Activity can be added to amorphous materials.

In some situations, strong mineral acids, such as HF, HCI, and H2SO, may be used directly to provide the desired acidity.
Or it can be used in the form of an aqueous or non-aqueous solution. Solid phosphoric acid is another substance that can promote the above-mentioned reactions.

Good compatibility substances are 100-100 as measured by α test,
It is a substance having acid activity of OOO, preferably 500 or more, and Am of 1000 or more.

Shape-selective zeolites with a control index of 1 to 12 are particularly desirable because of the formation of desirable products on the zeolites from oxygen-containing compounds. The shape selectivity of the zeolites also makes them resistant to aging (usually due to coke deposition), which occurs rapidly in conventional large pore zeolites.

The desired acid activity is obtained by mixing two different materials i', e.g. by mixing relatively highly acidic ZSM-5 or other materials with more inert compounds such as alumina or clay. be able to.

Also, less active materials can be used as long as the amount of acid ft material is supplemented and increased. Similar conversions can be obtained when adding 0.02% by weight of ZSM-5 with an alpha activity of 1600 or when adding 0.2% by weight of ZSM-5 with an alpha activity of 160.

Generally, the higher the temperature, the faster the catalytic and non-catalytic reactions. In other words, if the temperature is high,
Small amounts of catalyst are so effective that less catalyst is needed; the amount of catalyst must be balanced against the normally undesirable thermal decomposition that occurs naturally at high temperatures.

Residence time is also an important variable. Increasing the catalyst residence time (eg, lengthening the riser reactor) allows the use of lower acid activity catalyst or smaller amounts of catalyst.

-m requires more energy to obtain a high reaction temperature and, as a result, by providing a larger amount of catalyst, using a more acidic catalyst material, or providing a longer residence time. Attempts can be made to minimize the reaction temperature. Operating at relatively high temperatures is sometimes most advantageous, especially when a reforming-like reaction is desired.9 In order to make the reaction conditions stable and roughly thermally balanced reaction operation at high temperatures, It is desirable to use catalysts with lower acid activity, longer residence times, or smaller amounts of catalyst, so that thermally balanced reactions can be obtained at higher temperatures that promote reforming.

Also, by using a relatively large amount of a low acidity substance, a thermally balanced reaction can be carried out without catalyst regeneration. In the type of operation described above, ZSM-5 (or other stable acid active material) with a very high silica content can be provided in a fixed bed or preferably in a fluidized bed through which the feedstock and oxygen-containing compounds are passed. can. For low activity catalysts the presence of large amounts of catalyst can be tolerated, e.g. 0.1
L HS V based on a non-liquid charge corresponding to ~10, preferably 0.5 to 5 is a relatively low activity polymorphic material capable of carrying out the desired catalytic cracking reactions and oxygen-containing compound conversion reactions. provide a catalyst for performance. Large-scale dense-phase fluidized bed operation has some additional fl 1 points where the catalyst acts as a heat emitter and can minimize temperature fluctuations if problems occur when mixing the oxygen-containing compound and the oil. have. The above-mentioned problem will arise in case 3 where the two charges nl are not compatible or are difficult to mix.

Furthermore, it is difficult to mix oxygen compounds (which easily vaporize at low temperatures) with relatively heavy hydrocarbons (which are difficult to vaporize).

C3TR or continuous stirred tank reactor (ct+nLi
nious 5tirred tank reacto
In this type of operation, which can be considered an r) operation, the high acid activity of the zeolites is less important than the long-term stability of the zeolites, which minimizes the need for continuous regeneration.

Of course, a regeneration operation can also be performed, and a catalyst regeneration device can be installed close to the reactor. The catalyst regenerator does not act as a means to balance the heat of the unit; its primary purpose is to remove catalyst-deactivating coke from the catalyst. In an operation in which the nature of the catalyst regeneration operation is such that the amount of heat produced is less than the minimum amount of heat required for the regeneration operation, perhaps 10% or less of the required amount of heat, the amount of coke produced is extremely small. The heat from the combustion of can be recovered by heat exchange between the heat regeneration operation exhaust gas and the charged feedstock.

Another type of operation that can be performed is the use of a moving bed reactor. This design has also been investigated, but is considerably more complex than a fluidized dense phase reactor or a single packed bed reactor.

The process of the present invention frees the catalytic cracking process from relying on catalyst regeneration operations to maintain the thermal balance of the unit. Thermal equilibrium operations without regeneration operations can be achieved either by using a small amount of dispersed highly active catalyst (this operation was used in the example) or by providing a large amount of very stable, but perhaps somewhat less active, catalyst. This is achieved in two ways.

Prior Art In the past, methanol was added to the FCC feedstock, which closely resembled this concept.
．． 974.062 Q and U 3,974.063
In the FCC reaction in the above-mentioned patent, see #I18, maintenance of thermal equilibrium in the apparatus was due to the thermally regenerated catalyst. The addition of methanol did not significantly change the conversion of the charge to light products.

Continuous use of the catalyst of the prior art system results in approximately 1% coke build-up, which represents a loss of useful liquid products. Presumably, the large amount of catalyst present, i.e. 3mM% catalyst per ffi amount of oil, caused the early conversion of methanol to something else, unlike the present invention as disclosed in the examples. In the process, there is usually no catalyst present; more specifically, methanol is converted into l? The prior art method of adding CC charge l\ required 3 kg of catalyst per kg of oil charge; the method of the present invention required only 0.2 g of catalyst per kg of oil charge; Method 1 of the present invention
A 5,000 times larger amount of catalyst was used.

The thermal balance of the present invention eliminates the significant capital and operating costs of FCC regenerators, air compressors, etc. by liberating the catalytic cracking reaction from relying on catalyst regeneration operations as the means for the thermal balance reaction. This SO2 method does not generate SO2.
In conventional FCC regenerators, sulfur (present in the coke deposited on the catalyst) is always produced at the site of combustion. That is, the process of the present invention eliminates the significant air pollution problems associated with conventional catalytic cracking equipment, and eliminates the production of Zunawa SO and regenerator exhaust gases.

The products of the process of the invention are believed to have properties superior to conventional products obtained by catalytic cracking of hydrocarbons. One reason for this is that the conversion reaction is independent of reactor temperatures used in the past. The conversion reaction can be adjusted by increasing or decreasing the amount of catalyst added. The temperature in the reaction zone depends on the preheating of the charge rather than on the temperature and amount of regenerated thermal catalyst added to the reactor. Most can be determined.

[Brief explanation of drawings]

FIG. 1 is a schematic flow sheet of the catalytic thermal equilibrium cracking/conversion process, FIG. 2 is a graphical diagram showing the first order system for hexadecane cracking,
71 is a graph showing the Arrhenius plot for hexadecane cracking, FIG. 4 is a graph showing the Arrhenius plot for hexadecane cranking in reactors of different diameters, and FIG. 5 is a graph showing the Arrhenius plot for hexadecane cracking in reactors of different diameters. It is a graph diagram showing the relationship between propane/methane ratio based on weight 1, and the sixth
The figure is a graphical representation of Arrhenius propane for the cracking of hexadecane and hexadecane/methanol mixtures. In the diagram: 11... conduit, 12...
Conduit, 13... Conduit, 14... Conduit, 17... Conduit, 21... Conduit, 23... Conduit, 25... Heater, 26... Conduit, 27... Conduit, 28... Conduit, 2... Conduit, 31... Riser reactor, 3
3... Conduit, 35... Heat exchanger, 37... Conduit,
41... Rectifier, 43... Conduit, 47... Conduit, 4... Conduit, 51... Decanter-153...
Conduit, 55... Conduit. Fig, 2 Fig, 3 Fig, 4

Claims (1)

[Claims] 1. A method for producing lighter products by catalytic cracking of hydrocarbons with an acidic catalyst, which comprises cracking hydrocarbons, oxygen-containing carbon compounds, and hydrocarbons in a reactor; contacting an acidic catalyst capable of exothermically converting the oxygen-containing carbon compound to a hydrocarbon with increased carbon content, wherein at least a major proportion of the heat of reaction of the endothermic catalytic cracking reaction is directed to the hydrocarbon of the oxygen-containing carbon compound; A method for producing lighter products by catalytic cracking of hydrocarbons with an acidic catalyst, characterized in that the hydrocarbons are supplied by an exothermic reaction to 2. Claim 1 in which the reactor is a riser reactor
The method described in section. 3. The method according to claim 1 or 2, wherein the hydrocarbon is light oil. 4. The method according to any one of claims 1 to 3, wherein the oxygen-containing carbon compound is selected from the group consisting of lower alcohols, ethers, aldehydes, and ketones. 5. The method according to claim 4, wherein the oxygen-containing carbon compound is methanol. 6. The method according to any one of claims 1 to 5, wherein the catalyst is a zeolite. 7. The method according to claim 6, wherein the zeolite is HZSM-5. 8. A process according to any one of claims 1 to 7, wherein the zeolite is present in an amount equal to 0.01 to 5% by weight of the hydrocarbon. 9. The method of claim 8, wherein the zeolite is present in an amount equal to 0.02 to 1.0% by weight of the hydrocarbon. 10. A process according to any one of claims 1 to 9, wherein the reaction takes place at a temperature of 450 to 650°C and the hydrocarbon residence time in the reactor is 1 to 10 seconds. 11. The weight ratio of oxygen-containing carbon compound/hydrocarbon is 1/2
The method according to any one of claims 1 to 10, wherein the ratio is 0 to 2/1. 12. Premixing an oxygen-containing carbon compound and a catalyst to disperse the catalyst in the oxygen-containing carbon compound, and then mixing the resulting mixture with a hydrocarbon.Claims 1 to 11
The method described in any one of the preceding paragraphs. 13. The method according to any one of claims 1 to 12, wherein the catalyst is ZSM-5 with an α activity of 500 or more, and the catalyst particle size is 50 microns or less.