EP0344376A1

EP0344376A1 - Process for converting heavy hydrocarbons to lighter hydrocarbons

Info

Publication number: EP0344376A1
Application number: EP88306021A
Authority: EP
Inventors: Ching Piao Lin
Original assignee: Individual
Current assignee: Individual
Priority date: 1988-06-03
Filing date: 1988-07-01
Publication date: 1989-12-06

Abstract

A process for converting a heavy crude oil feed into lighter fraction products comprising:

A. introducing an amount of catalyst and the feed into a liquid phase reactor at a temperature in the range of about 300°C to about 500°C at a pressure in the range of about 1 to about 20 atms for a residence time of about 1 sec to about 5 minutes;
B. contacting the resultant products with superheated steam; and
C. then separating the resultant light fraction products from coke.

Description

Generally speaking, commercial crude oils are distilled at atmosphere pressure to a boiling point of about 340°C to recovery light fractions which are useful, such as naphtha, gasoline, kerosine, and heating oil. The heavier nonvolatile fractions, which distill above about 340°C, forms the so called atmospheric residues. The amount of the atmospheric residues is about 40% to about 60% of the total crude oils as shown by assay results from commercial plant operations. The relatively abundant atmospheric residues are, however, unsuitable for inclusion in naphtha, gasoline and other liquid hydrocarbons without further conversion.
To solve the above problem, various heavy oils conversion processes have been developed, such as vacuum distillation, visbreaking, delayed coking, hydrotreating, hydrocracking, and fluidized catalytic cracking (FCC) as well as other approaches of reduced crude conversion. Among these, FCC is predominant in most refineries and is far-reaching in influencing the cost and qualities of the products.
Although the FCC process is now a highly sophisticated process and many modifications and variations have been developed, many limitation for its utilization still exist. Example of these include limitations in the concentrations of contaminating materials in the starting crude oils: sulfur; light metals, such as sodium and potassium; heavy metals such as nickel, vanadium, iron and copper; coke precursors such as asphaltenes and polynuclear aromatics and nitrogen.
It is generally known that, for FCC processing, the concentrations of the various materials in the feed should be limited to the following: sulfur, from about 0.15 weight & ("wt %") to about 1.5 wt %; for heavy metals, from about 0.1 ppm to about 100 ppm of nickel and/or its equivalents; sodium, from 1 to about 8ppm; conradson carbon content, from about 1 wt % to about 12 wt %.
Some of these undesirable materials can be removed by a specific purification steps which, however, add to the cost. For example, light metals such as sodium and other alkaline earth metals can be removed by a desalting operation. Sulfur and its compounds can effectively be removed by hydrotreating or hydrocracking. Other materials, however, cannot be effectively removed and will adversely affect the activity level of the catalyst used in FCC. For example, coke precursors tend to breakdown into coke which deposits on the surface of the catalyst and reduce the level of catalyst activity. Heavy metals, such as vanadium, tend to form fluxes which lower the melting point of catalyst and thus render the catalyst ineffective. Accumulation of other metals, especially nickel, poisons the catalysts, which tend to reduced gasoline yield and at the same time increase the formation of carbon and C4-gases.
Other heavy oil conversion processes also suffer from one disadvantage, in that the cracking temperature of these processes is generally between 500°C and at these temperature about 20 to 25 wt % C4-gases are generated. Thus, to improve the amount of gasoline produced, further conversion by hydrotreating, reforming or alkylation is required. These operations also can increase capital investment and operation cost.
The atmospheric residues contain high concentrations of the above-mentioned contaminants and, in general, cannot be directly used as feed for FCC. The art has developed some processes such as visbreaking, delayed coking, deasphalting, hydrotreating, and hydrocracking for reduced contaminants. These processes, however, further increase the capital investment and operating cost.
In addition to the processed petroleum crude oil previously described, there are natural extra heavy oils such as bituments, shale oils and oils from coal liquefactions, which cannot be economically processed up to the present. Currently, more than 90% of world demand is supplied by light and medium crude oil. However, these account for less than 25% of the remaining petroleum resources. Therefore, future demand will have to be met increasingly with various forms of extra heavy oils.
At present, naturally occurring or synthetic polymers such as wasts cables, wasts plastics and scrap tires and coals such as bituminous coal and sub bituminous coal herein defined as solid hydrocarbons are not economically converted to light hydrocarbon products. The accumulations of large quantities of these waste polymers result in environmental and health problems. It is, therefore, highly desirable to convert these waste polymers to useful light hydrocarbons.
In brief, it appears there is room for improving the presently available processes and catalysts for economical conversion of petroleum heavy crude oils, natural extra heavy oils and solid hydrocarbons into useful light hydrocarbons.

SUMMARY OF THE INVENTION

Accordingly, it is an object of this invention to provide a novel process and catalyst for converting heavy crude oils and/or solid hydrocarbons to gasoline and other light fraction products without placing severe restrictions on the quality of the feed such that a more versatile process with reduced capital investment and operation cost is realized.
It is another object of this invention to provide a novel process and catalyst for converting heat crude oils and/or solid hydrocarbons to gasoline and other lighter fraction products without generating a high amount of C4-gases and coke.
It is yet another object of this invention to provide a novel process and catalyst for directly converting crude oils and atmospheric residues into gasoline and other light fraction products by catalyst cracking without the need to remove the contaminants of the crude oils and atmospheric residues in advance.
It is a further object of this invention to provide a novel process and catalyst for improving the performance of catalytic cracking of heavy crude oils to gasoline and other light fraction products in a conventional moving bed reactor regenerator system, such as a FCC unit.
It is yet a further object of this invention to provide a novel process and catalyst for converting heavy crude oils to gasoline and other light fraction products which can be incorporated into existing petroleum refinery operations in an economical manner.
The present invention in its broadest context encompasses a process and catalyst for converting heavy crude oils and/or solid hydrocarbons to gasoline and other light fraction products in a liquid phase reactor or in a fluidized catalytic cracking converter comprising the steps of:

A. providing a feed comprising heavy crude oils and/or solid hydrocarbons;
B. contacting the feed with a catalyst selected from the group consisting of metal alkoxides, phenoxides and mixtures thereof in a liquid phase or a gas solid system at a temperature from about 250°C and a pressure of from about 1 to about 20 atms, for a residence time from about 1 sec to about 30 minutes;
C. contacting the resultant products with superheated steam at a temperature of about 300°C to about 500°C and a pressure of from about 1 to about 10 atms with a residence time of 0.1 sec to about 5 minutes; and
D. separating the resultant light hydrocarbons and coke products by using a gas solid separating system.

BRIEF DESCRIPTION OF THE DRAWINGS

Fig. 1 is a schematic flow diagram of the process of the present invention for the catalytic conversion of heavy crude oils.
Fig. 2 is a schematic flow diagram of an improved petroleum refinery operation incorporation the catalytic conversion process of the present invention.
Fig. 3 is a schematic flow diagram of the process of the present invention for the catalytic conversion of solid hydrocarbons.
Fig. 4 is a schematic flow diagram of an improved fluidized bed catalytic conversion process of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The process of the present invention for converting heavy crude oils and/or solid hydrocarbons to gasoline and other lighter fraction products comprises the steps of:

A. providing a reactor feed comprising heavy crude oils and/or solid hydrocarbons;
B. contacting the feed with a catalyst selected from the group consisting of metal alkoxides, phenoxides and mixtures thereof at a temperature of from about 250°C to about 500°C and a pressure of from about 1 to about 20 atms with a residence time of from about 1 sec to about 30 minutes;
C. contacting the resultant products with superheated steam at a temperature of about 300°C to about 500°C and a pressure of from about 1 to 10 atms for a residence time of about 0.1 sec to about 5 minutes; and
D. separating the resultant light hydrocarbons and coke by a gas solid separating system.

The individual elements of the present invention are described in detailed below.

Feed

The process of the present invention can use various heavy crude oils as feed, whether they are of petroleum origin or not. The various heavy crude oils include widely diverse material, such as crude oils as removed from the well, atmospheric residues containing distillates above about 340°C from a crude oil distillation column. The feed is composed of fairly high molecualr weight materials of very complex chemical character. Crude oils and atmospheric residues usually contain a high proportion of total nitrogen, sulfur and metals. Other feeds include heavy crude from vacuum residues, extracts from solvent deasphalting, aromatic extracts from lube refining, tar bottoms, heavy cycle oil and other refinery waste strams, as well as naturally occurring extra heavy oils, shale oils, tar sand extracts, oil from coal liquefactions, bitumen crude oil and mixtures of the foregoing. The feed can be directly converted to light hydrocarbons without pre-treating such as demetalation, desulfurization, and decarbonization or the passivation of heavy metals in a fluidized catalytic cracking unit.
The process of the present invention is also applicable to various solid hydrocarbons. The solid hydrocarbons include widely diverse materials; synthetic polymers, such as polyethylenes, polyvinyls, polystyrenes, polyamides and polyesters; elastomers, including SBR, butyl rubber, natural rubbers and polychloroprene; coals, including bituminous coal and sub bituminous coal; and waste streams from waste plastic, waste cable, scrap tires and the like. Mixtures of the foregoing may also be used as feeds. These solid hydrocarbon feeds may have a sulfur content, high chloride content, high nitrogen content and high metals content. But additional purification to remove the contaminants prior to conversion is not required. The particle size of the solid hydrocarbons is preferably about 1 mm. to about 50 mm. The solid hydrocarbons is admixed with the catalyst and liquid hydrocarbons to from a paste or slurry. The liquid hydrocarbons can be recycled oils formed in the conversion or any heavy oils such as Virgin Gas Oil, Light cyclie Oil, atmospheric residues and crude oils.

Catalysts

The catalysts suitable for the process of the invention is a particulate catalyst comprising metal alkoxides and/or phenoxides as the active ingredient. The organometallic compound is represented by the formula:
M(OR)_n
wherein
M represents a metal selected from the group consisting of groups IA, IIA, IIIA, IVA, IB, IIB, and IVB of the Periodic Table;
OR is a alkoxy functional group derived from Grignard reagents, phenols, ethers or from primary, secondary, or tertiary alcohols;
n is 1, 2, 3, or 4; and
R represents alkyl, cycloalkyl, phenyl, or allyl with 1 to 10 carbon atoms.
The selected catalyst is soluble in the feed or in a hydrocarbon solvent miscible with the feed. Suitable solvents are Virgin Gas Oil, Light Cycle Oils, Heavy Gas Oil, naphtha, alcohols, aromatic and organic solvents. The amount of the catalyst effective to convert said feed to light fraction hydrocarbons is about 0.001 wt % to about 1 wt % based on the total weight of the heavy crude oil and/or solid hydrocarbons. The catalyst may be introduced in any suitable fashions. For instance, they may be admixed with crude oils before the atmospheric distallation column or admixed with atmospheric residues from the bottom of the distillation column. The catalyst may, if desired, be admixed with atmospheric residues before or after the furnace for delayed coking and visbreaking. Alternatively, the catalyst may be admixed with the feed prior to being contacted with carrier particles later into the cracking zone, or be deposited with carrier particles prior to being contacted with the feed later into the cracking zone.
The catalyst, when used in accordance with this invention in a gas solid system such as in fluidized catalytic cracking, is continuously contacted with the feed and carrier particles in the cracking zone. The composition of the solid carrier particles useful in this invention is not critical, provided that such carrier particles are capable of promoting the desired final hydrocarbon conversion.
Carrier particles having widely varying compositions, conventionally used as carriers in hydrocarbon conversion can be used. Such suitable materials include natural clay such as montmorillonite, kaolin and bentonite clays, natural or synthetic amorphous materials, such as amorphous silica/alumina, silica/magnesia and silica/zirconia composites; and an alternative of coke and carbon.
The carrier particles can be solid particles or discrete entities. This is not critical to the present invention. It may depend on the type of fluidized reactor-regenerator system employed. Such carrier particles may be formed into any desired shapes, such as pills, cakes, powders, granules and the like using conventional methods.
For a fixed bed system, the catalyst with a particle size of 0.25 mm to about 6 mm may be used. For a fluidized bed system, it is preferred that the catalyst particles have a diameter in range of about 10 microns to about 650 microns.
It will be recognized by one skilled in the art that the catalyst of this invention described above are all well deposited one coke or loaded on carrier particles and are difficult to separate from the reaction mixtures, and also that these catalysts can not be regenerated.

Reaction

The cracking reaction of the present invention is carried out at a temperature of from about 250°C to about 500°C, preferably from about 350°C to about 450°C, and a pressure of from about 1 to about 20 atms. When solid hydrocarbons are to be converted, a residence time of from about 1 minute to 30 minutes is required. The residence times for liquid feeds can be lower, from about 1 sec to about 5 minutes. The resultant products, including light fraction hydrocarbons and coke, are further contacted with superheated steam at a temperatures of about 300°C to about 500°C and a pressure of about 1 to about 10 atms for a residence time of about 0.1 sec to about 5 minutes.
The preferred liquid phase reactor, contemplated by the present invention, may be a tank, a tubular reactor of a tower, and are described in "Perry's Chemical Engineers' Handbook". When incorporated with an existing petroleum refinery system and to maintain the reaction in a liquid phase, the tank, or tubular reactor, or tower or furnace, or the bottom of the distillation column, is maintained at a temperature of from about 350°C to about 450°C and a pressure of about 1 to about 20 atms.
The preferred gas solid converter of this invention is a conventional fluidized catalytic cracking unit. The catalyst is admixed with feed prior to being contacted with carrier particles from the regenerator later into the cracking zone. The cracking reaction is carried out both in liquid phase and gas solid phase at a temperature of from about 350°C to about 500°C for a residence time of about 1 sec to about 5 minutes. The spent, coke and catalyst laden carrier particles are separated from the stream of the resultant cracked products, and regenerated in regeneration beds by burning the coke on the spent catalyst particles with oxygen. The regenerated hot carrier particles is recycled to the cracking zone to be contacted with feed and catalyst mixtures.
It is contemplated that the invention although described herein only in relation to existing commecial FCC units, will also be applicable to any conventional reactor regenerator system, e.g., a fixed bed catalyst conversion regenerator system, a ebullition catalyst system, a system wherein the carrier particles are continuously circulated between the reaction zone and the regeneration zone, and the like.

Separation

Any separation operation, which can effectively separate the light hydrocarbons and coke from the other cracked products, such as described in "Perry's Chemical Engineers' Handbook", is contemplated to be useful in the present invention. In one preferred embodiment, the product mixture of light hydrocarbons and coke is admixed with superheated steam and is sprayed into a spray drying unit, or a cyclone separator, or a delayed coking unit. In another preferred embodiment, a conventional fluidized catalytic cracking unit is used. Any conventional reactor regenerator system may also be applied, e.g., a fixed bed catalyst conversion regenerator and separator system in a ebullition catalyst conversion and separation system, or a system which continuously circulates carrier particles between the reaction zone and the regeneration zone, or the like. The atomizing fluid for the foregoing separation is superheated steam or hot carrier particles at a temperature of about 350°C to about 500°C.
It is contemplated that the invention described herein can be incorporated into an existing petroleum integrated refinery operation such as a delayed coking unit, a visbreaking unit, and a fluidized catalytic cracking unit. The preferred embodiment will be described with reference to the drawings.
Referring to Fig. 1, a liquid hydrocarbon, for example heavy crude oils, is introduced via 1 together with the catalyst from 2 into a tubular reactor 4, which is operated at a temperature of about 350°C to about 450°C and maintained at a pressure for about 1 to about 7 atms via 5. The residence time in the tubular reactor is about 1 sec to about 5 minutes. The resultant light hydrocarbons and coke are withdrawn from 7 and contacted with superheated steam via 8 at 350°C to 450°C and fed into separator 9. The vaporized light hydrocarbons mixed with steam is withdrawn from 10 to a fractionator. The coke is withdrawn from 11.
It is contemplated that the invention described in Fig. 1 pertaining to foregoing system can be modified to be applicable to any existing integrated refinery operation in a suitable fashion. For example, in Fig. 2, the atmospheric residues 1 are admixed with the catalyst from 12 and fed into the furance 14 where the temperature is allowed to rise to a preset point for a preset residence time in a tubular reactor 15 for hydrocarbon conversion. The resulting cracked products are contacted with superheated steam 16 and fed into the delayed coking unit 17. The vaporized light hydrocarbons mixed with steam is withdrawn from 19 and fed to distallation column 20, and coke is withdrawn from 18.
Referring to Fig. 3, crushed polymers, for example, such as waste tires, waste cables, waste plastic and coals together with heavy crude oils or recycle oils from a conversion process and catalyst via 21, 22, 23, is introduced into a tubular reactor 24 under cracking conditions at a temperature range of about 350°C to about 450°C for a residence time about 1 to about 30 minutes. The pressure in the tubular reactor is maintained via 25 in a range of about 1 to about 7 atms. Any waste steel and copper wires are withdrawn from 26. The waste steel and copper wires are withdrawn from 26. The cracked light fraction products and coke are fed via 27 and contacted with superheated steam via 28 at 350°C to 450°C and brought into separator 29. The light fractions mixed with superheated steam are withdrawn from 30 for fractionating. The coke is withdrawn from 31.
referring to Fig. 4, a conventional fluidized catalytic cracking unit can be improved by introducing feed via 41 together with catalyst via 32 into tubular reactor 3 at a temperature from about 350°C to about 450°C and a pressure from about 1 to about 7 atms for a residence time from about 1 sec to about 5 minutes. The mixture of feeds is further contacted with carrier particles via 38 into the cracking zone 35. The cracked light hydrocarbons and spent coke is separated in the reactor. The coke laden particles are withdrawn via 36 and fed into regenerator 37 for removing the coke by burning with oxygen. The vaporized light fractions is withdrawn from 50 for further fractionating. The temperature of the carrier particles is maintained in a range from about 350°C to about 500°C. The catalyst may, if desired, by mixed with the carrier particles prior to being contacted with feed later into the cracking zone such as via the dotted line from 32.
The catalyst used for the foregoing described hydrocarbon conversion process is in an amount of about 0.001 to about 1 weight percent of feed, preferably about 0.001 to about 0.1 weight percent of feed.
The present invention will be more fully understood from the following examples, which are for the purpose to illustrate preferred embodiments of the invention. The examples are not to be construed as limiting the scope of the invention.

EXAMPLE 1

Catalyst A

Twenty-seven grams of aluminum wire and foil is placed in a one liter round-bottomed flask containing 300 cc of propyl alcohol and 0.5 g of mercuric chloride. The flask is attached to a reflux condenser, which is protected from moisture by a calcium chloride drying tube. The mixture is heated on a steam bath. When the liquid is boiling, 2 cc of carbon tetrachloride, an effective catalyst for the reaction, is added through the condenser, and heating is continued. The mixture turns gray, and in a few minutes a vigorous evolution of hydrogen begins. At this point, it is necessary to discontinue heating, and frequently moderate the reaction by cooling the flask in ice water. After the reaction has slackened, refluxing is resumed and is continued until all of the aluminum has dissolved. The resultant catalyst is dissolved in a solvent at a ratio by weight of 1 to 10.

Catalyst B

Twenty-three grams of sodium is placed in a one liter round-bottom flask containing 150 cc of butyl alcohol. The flask is attached to an reflux condenser which is protected from moisture by a mercury trap or calcium chloride tube. In a few minutes a vigorous evaluation of hydrogen begins. It is necessary then to frequently moderate the reaction by cooling the flask with ice water. After the reaction has slackened, and all sodium has dissolved, the resultant product is dissolved in suitable solvent at weight ratio of 1 to 10.

Catalyst C

Forty grams of NaOH is placed in one liter round bottomed flask containing 120 grams phenol. The mixture is heated on a water bath. In a few mitures the mixtures turns clear. The resultant product is dissolved in a suitable solvent at a weight ratio of 1:5.

EXAMPLE II

300 grams of atmospheric residues and an amount, as shown in Table 1, of one of the prepared catalyst are placed in a one liter tubular reactor in a tube furnace. Heat and pressure are applied to increase the temperature and pressure to a preset level. After the desired residence time is reached, the reactor is purged with nitrogen and in an amount sufficient to separate the light fraction hydrocarbons from coke. The characteristics of the feed, the cracking conditions, and resultant products are presented in Table 1.

Table 1

Test No.	1	2	3
API Gravity	23	19.4	19.4
Sulfur, % wt	7.2	1.74	1.74
Conradson carbon, % wt	7.5	6.68	6.68
Nickel eqivalents, ppm wt	1260	38.76	38.78
Nitrogen, % wt	-	0.07	0.07
BSW, % wt	1.5	1.5	1.5
Catalyst	A	A	B
Catalyst wt % on feed	0.04	0.04	0.04
Cracking temperature, C	402	380	375
Pressure, atm	4.5	4.0	3.0
Residence time, minutes	5	5	5
Gases, % wt	9.40	6.3	16.23
Light fractions, % wt	82.81	85.7	71.63
Sp. Gravity of light oil	0.86	0.87	0.87
Coke, % wt	7.79	8.00	12.24

EXAMPLE III

To illustrate extra heavy oils conversion, asphaltene and tar as feed is tested. 300 grams of feed with catalyst is placed into a one liter tubular reactor at a preset temperature and pressure. After the desired residence time is reached, nitrogen is introduced into the tubular reactor in an amount sufficient to separate the light fraction hydrocarbons from coke. The cracking conditions, characteristics of the feeds and the cracked products are presented in Table 2.

Table 2

Test No.	4	5	6
Feed	Asphaltene	Asphaltene	Tar
	MC-150	MC-180	-
Conradson carbon % wt	22.8	7.1	21.2
Catalyst	A	A	C
Catalyst, wt %	0.04	0.04	0.04
Cracking temperature, C	400	400	400
Pressure, atm	3.5	3.5	1.
Residence time, minutes	5	5	5
Gas, % wt	11.46	7.25	6.2
Light fractions, % wt	67.60	81.86	67.5
Sp. Gravity of light oil	0.88	0.87	0.865
Coke, % wt	20.94	10.87	26.3

EXAMPLE IV

To illustrate the solid hydrocarbons conversion process, waste cables, waste tires, and coal are prepared as feed. The waste cables and waste tires are crushed to a size of less than 25 mm and coal is ground to a size of less than 1 mm. The feed and catalyst a combined with atmospheric residues from test No. 2 or gas oil are placed in a one liter tubular reactor in a tubular furnace. Heat is applied and the reactor pressurized to preset temperature and pressure. After a preset residence time is reached, nitrogen is introduced into the tubular reactor in an amount sufficient to separate the light fractions from coke and metal wire. The properties of the feed, the operation conditions and resultant products are presented in Table 3.

Table 3

Test No.	7	8	9
Solid hydrocarbons	Tires	Cables	Coal
Liquid hydrocarbons	Atmos. Resid.	Atmos. Resid.	Gas Oil
Solid : Liquid Ratio	1 : 1	1 : 1	1.75 : 1
Carbon, % wt	82.93	-	67.79
Hydrogen, % wt	7.02	-	3.13
Oxygen, % wt	2.19	-	9.04
Nitrogen, % wt	0.24	-	0.56
Sulfur, % wt	1.23	-	0.43
Ash, % wt	4.75	-	15.66
Moisture, % wt	1.50	-	3.39
Catalyst, % wt on feed	0.023	0.04	0.078
Cracking temperature, C	350	350	395
Residence time, minutes	10	10	10
Gas, % wt	3.55	5.94	13.40
Light fractions, % wt	80.22	42.24	56.76
Coke on all feed, % wt	16.23	11.25	29.84
Coke on solid hydrocarbon, % wt	23.7	11.25	44.80
Waste metal wire, % wt	-	40.57	-

EXAMPLE V

To illustrate gas solid conversions, a portion of a catalyst is mixed with atmospheric residues from test No. 2 and heavy gas oil, and another portion of a catalyst is deposited on the coke particle from test 7. A tubular reactor in a tube furnace is filled with catalyst deposited coke particles. The reactor is attached to a condenser and a nitrogen purger. Heat is applied to a preset temperature and the feed is introduced by a syringe pump to be contacted with the catalyst particles. The resultant cracked products are continuously withdrawn from the condenser. At end of the process, nitrogen gas is introduced to further separate light fractions from coke. The results are shown in Table 4.

Table 4

Test No.	10	11
Feed	Gas oils	Atmospheric residues
API	26.3	19.4
Catalyst	A	A
Catalyst wt, % in feed	0.02	0.02
Catalyst wt, % in particles	0.1	0.1
Pressure, atm	0.8	0.8
Cracking Temperature, °C	405	425
Space velocity, W/W/min	0.38	0.38
Particles : oil ratio	3 : 1	3 : 1
Gas, wt %	7.28	7.33
Light fractions, wt %	90.1	85.0
Sp. Gravity light oil	0.85	0.86
Coke, wt %	2.62	7.67

EXAMPLE VI

A portion of the light fraction products and coke from Test No. 2, Test No. 7 and Test No. 8 is treated and separated by superheated steam of 350°C. The resultant light fractions is stilled in a Thermogravimetric Analyzer. The results of the distillation is illustrated in Table 5.

Table 5

Sample from	Test No. 2	Test No. 7	Test No. 8
50°C, wt %	0	0	0
100°C, wt %	3.86	5.96	11.93
150°C, wt %	10.88	14.74	31.23
200°C, wt %	23.51	28.77	54.74
250°C, wt %	44.21	51.23	69.12
300°C, wt %	72.28	79.30	84.91
350°C, wt %	91.23	94.04	94.04
400°C, wt %	96.49	95.78	97.54
450°C, wt %	97.54	96.84	98.94

EXAMPLE VII

A commercial fuel oil was used as the feed in the cracking operations in the following tests and had the following characteristics: API gravity 21; sulfur 2.5 st %; conradson carbon number 6.33; nickel equivalent metals 120 ppm. 300 grams of the feed and 0.2 cc of catalyst A is placed in a one liter tubular reactor in a tube furnace and heat and pressure were applied to a preset temperature and pressure. After a preset residence time is reached, the resultant products of Test No. 12 is contacted with superheated steam at 350°C; and the resultant products of Test No. 13 is contacted with nitrogen at 350°C. The data are shown in Table 6 below. Treatment with superheated steam reduced the amount of coke formed by about 50%. Table 6

Test No. 12 13

Cracking temperature, °C 395 395

Cracking pressure, atm 3.0 4.0

Residence time, sec. 3.0 3.0

Coke, wt % 3.24 7.14

Claims

1. A process for converting a heavy crude oil feed into lighter fraction products comprising:

A. introducing an amount of catalyst and the feed into a liquid phase reactor at a temperature in the range of about 300°C to about 500°C at a pressure in the range of about 1 to about 20 atms for a residence time of about 1 sec to about 5 minutes;

B. contacting the resultant products with superheated steam; and

C. then separating the resultant light fraction products from coke.

2. A process according to claim 1, wherein said pressure is sufficient to keep the reaction mixture in liquid phase.

3. A process according to claim 1 or 2, wherein the said reactor is a tubular reactor.

4. A process according to claim 1, 2 or 3, wherein the said superheated stem is at a temperature in the range of about 300°C to about 500°C and a pressure in the range of about 1 to about 10 atms, and the residence time is about 0.1 sec to about 5 minutes.

5. A process according to any one of claims 1 to 4 wherein the light fraction products are separated by contacting the resultant light fraction products including coke with an atomizing fluid of superheated steam or hot carrier particles at a temperature from about 350°C to about 500°C.

6. A process for converting a heavy crude oil feed into lighter fraction products comprising:

A. admixing an amount of catalyst with the feed and then contacting the mixture in a cracking zone under cracking conditions in the liquid phase and gas solid phase under a lower temperature, with carrier particles from a regeneration zone;

B. separating particles having coke deposited thereon from the effluent;

C. introducing the particles with coke deposited thereon into a regeneration zone to remove the coke by burning with oxygen; and

D. recycling the carrier particles to the cracking zone.

7. A process according to claim 6, wherein the said temperature is in the range of about 300°C to about 500°C and the pressure in the liquid phase reactor is in the range of 1 to 20 atms and the pressure in the gas solid converter is in the range of about 1 to about 3 atms.

8. A process according to any of claims 1 to 7, wherein the said feed is untreated crude oil; atmospheric or other residue from crude oil; reduced crude comprising light gas oil and heavy gas oil; shale oil; heavy bitumen crude oil; tar sand extract; or an oil from coal liquefaction.

9. A process for converting a solid hydrocarbon feed into lighter fraction products comprising;

A. introducing an amount of catalyst and the feed with liquid oil into a liquid phase reactor at a temperature in the range of about 250°C to about 500°C and a pressure in the range of about 1 to about 20 atms for a residence time of about 1 to about 30 minutes;

B. contacting the resultant products with superheated steam; and

C. separating the resultant light fraction products and coke.

10. A process according to claim 9, wherein the said solid feed comprises one or more polymers and elastomers in the form of scrap tires, waste cables, or waste plastics; or coal including bituminous coal and sub bituminous coal.

11. A process according to claim 9 or 10, wherein the said liquid oil is crude oil, gas oil, atmospheric residues or recycle oil.

12. A process according to any of claims 9 to 11, wherein the said solid feed and the liquid oil are in a ration such as to form a paste or slurry.

13. A process according to any of claims 9 to 12, wherein the said reactor is a tank reactor or a tubular reactor.

14. A process according to any of claims 9 to 13, wherein the said superheated steam is at a temperature in the range of about 300°C to about 500°C, a pressure in the range of about 1 to about 10 atms and a residence time of about 0.1 sec to about 30 minutes.

15. A process according to any of claims 9 to 14, wherein the light fraction products are separated from coke by contacting the resultant light fraction products and coke with an atomizing fluid of superheated steam or hot carrier particles at a temperature in the range of about 300°C to about 500°C.

16. A process according to any of claims 1 to 15, wherein the said catalyst is a metal alkoxide and/or phenoxide wherein the metal is selected from the group consisting of groups IA, IIA, IIIA, IVA, IB, IIB, and IVB metals of the periodic table.

17. A process according to any of claims 1 to 16, wherein the amount of said catalyst is in the range of about 0.001 to about 1 weight percent of the feed.