US3728252A - Desulfurization of heavy liquid hydrocarbon with carbon monoxide at high pressure - Google Patents

Abstract

A HEAVY HYDROCARBON FEEDSTOCK IS UPGRADED BY AT LEAST ONE OF THE PROCESS OF DESULFURIZATION, DECREASING CARBON RESIDUES, INCREASING API GRAVITY, AND LIQUEFACTION OF SOLID FEEDSTOCK BY REACTING THE FEEDSTOCK AT ELEVATED TEMPERATURE AND PRESSURE IN THE PRESENCE OF CARBON MONOXIDE AND IN THE PRESENCE OF A CATALYTICALLY ACTIVE METAL. IN ONE EMBODIMENT THE ACTIVE METLLIC CATALYST IS ASSOCIATED WITH MINOR AMOUNTS OF ALKALI OR ALKALINE EARTH METALS TO MINIMIZE PROMOTION OF CRACKING SIDE REACTIONS. IN A PREFERRED EMBODIMENT A HEAVY HYDROCARBON FEEDSTOCK IS UPGRADED IN THE PRESENCE OF THE CATALYST SYSTEM FORMED FROM A BARIUM SALT WHICH HAS BEEN DEPOSITED ON COBALT MOLYBDATE DISPERSED ON AN ALUMINA SUPPORT.

Description

United States Patent Office 3,728,252 Patented Apr. 17, 19,73

ABSTRACT OF THE DISCLOSURE A heavy hydrocarbon feedstock is upgraded by at least one of the processes of desulfurization, decreasing car-bon residues, increasing API gravity, and liquefaction of solid feedstock by reacting the feedstock at elevated temperature and pressure in the presence of carbon monoxide and in the presence of a catalytically active metal. In one embodiment the active metallic catalyst is associated with minor amounts of alkali or alkaline earth metals to minimize promotion of cracking side reactions. In a pre ferred embodiment a heavy hydrocarbon feedstock is upgraded in the presence of the catalyst system formed from a barium salt which has been deposited on cobalt molybdate dispersed on an alumina support.

CROSS-REFERENCES TO RELATED APPLICATIONS In my co-pending application Ser. No. 757,113, filed Oct. 3, 1968, now Pat. No. 3,586,621 is disclosed amethod for desulfurizing heavy hydrocarbon feeds by contacting such feeds with steam in the presence of suitable catalysts. The effectiveness of that process is believed to be due to the occurrence of reactions such as the water-gas shift reaction and the hydrogenation reaction.

It has now been found that still more improved results can be obtained by contacting heavy hydrocarbon-containing feeds with carbon monoxide in either the presence or absence of steam over suitable catalysts. Not only are beneficial results obtained at temperatures which are generally lower than those of the above-described filed case, but also benefits other than desulfurization are obtained.

BACKGROUND OF INVENTION This invention relates to the upgrading of heavy hydrocarbon feedstocks. In one of its aspects, this invention relates to multiple purpose catalysts. In another of its aspects, this invention relates to effecting multiple reactions with a single catalyst system. In still another of its aspects, this invention relates to desulfurization of hydrocarbon feedstocks. In still another of its aspects, this invention relates to decreasing carbon residues in hydrocarbon feedstocks. In yet another of its aspects, this invention relates to liquefaction of solid hydrocarbons in feedstock materials. In yet another of its aspects, this invention relates to increasing the API gravity of hydro carbon feedstocks.

In one of its concepts, this invention provides a method for performing at least one reaction chosen from: desulfurizing a hydrocarbon feedstock, decreasing the carbon residues in a hydrocarbon feedstock, increasing the API gravity of a hydrocarbon feedstock, or liquefying a solid hydrocarbon in hydrocarbon feedstock material using an active metal catalyst. Another of its concepts, this invention provides a method for simultaneously catalyzing multiple chemical reactions using active metal catalysts.

Catalytic methods that can desulfurize, increase the API gravity, or decrease the carbon residues in hydrocarbon feedstocks are known. Methods for liquefying solid hydrocarbons and hydrocarbon feedstocks are also known.

These known methods are, however, directed to specific reactions and do not possess the versatility of generally upgrading a hydrocarbon feedstock by promotion of a combination of reactions.

It is therefore an object of this invention to provide an economical method for the upgrading of hydrocarbon feedstocks. It is another object of this invention to provide a method for effecting a multiple upgrading of hydrocarbon feedstocks.

Other aspects, concepts and objects of the invention are apparent from the study of this disclosure and the appended claims.

SUMMARY OF THE INVENTION According to the present invention there is provided a method for upgrading heavy hydrocarbon feedstock which comprises reacting the feedstock at an elevated temperature and pressure in the presence of carbon monoxide and in the presence of an active metal selected from molybdenum, tungsten, nickel, cobalt, copper, iron, and zinc.

In a further embodiment of this invention the reaction of the feedstock at an elevated temperature and pressure takes place in the presence of carbon monoxide and an active metal catalyst from the list above and steam.

The process of the invention will upgrade the applicable feedstocks in one or more ways. The process can substantially desulfurize the feedstocks. It can decrease the carbon residue and increase the API gravity of a crude oil. It can reduce the sulfur content of a coal and/ or convert a substantial portion of a coal to liquid hydrocarbon products.

The above benefits can be obtained Without the need coke formation and with relatively low formation of cracked low molecular weight byproducts.

The feedstocks which can be upgraded according to the process of the invention are heavy hydrocarbon-containing feedstocks. These can be crude oils, heavy hydrocarbon oils, residual hydrocarbon fractions, as well as solid carbonaceous materials such as coal. These feedstocks can contain aliphatic and aromatic hydrocarbons as well as acyclic and alicyclic paraffius and olefinic compounds such as those containing up to 40 or more carbon atoms per molecule or those having molecular weights as high as 500 or more. The feedstock can also comprise pulverized coal dispersed in a hydrocarbon oil particularly in a hydrocarbon oil capable of participating in hydrogen exchange reactions as a hydrogen donor, such as an aromatic oil or a hydrogenated aromatic oil. The heavy hydrocarbon-containing feedstocks will generally be naturally occurring and will generally contain a substantial sulfur content, although any crude oil and any coal, including bituminous and anthracite, is applicable.

The catalysts which are applicable for use in the present invention are those which contain catalytically active metals selected from molybdenum, tungsten, nickel, cobalt, copper, iron, zinc, and mixtures thereof. These elements can be present in the metallic state or in the form of oxides, or carbonyls, or sulfides, or salts of carboxylic acids such as naphthenic acids, or chemically combined with each other, or chemically or physically combined with other metals such as the alkali or alkaline earth metals, particularly barium. Some examples of these are molybdenum oxide, cobalt molybdate, nickel sulfide, zinc molybdate, copper oxide barium oxide, copper molybdate, magnesium tungstate, iron oxide barium molybdate, tungsten oxide, zinc sulfide, molybdenum hexacarbonyl, cobalt oxide, cobalt naphthenate, nickel naphthenate, barium naphthenate, and the like and mixtures thereof.

Such catalytically active materials can be associated,

the non-acidic type, such as alumina, calcium aluminate, barium aluminate, magnesium aluminate, bauxite, and the like and mixtures thereof. When such support ma- The conversion temperature will generally be in the range of from about 550 to about 800 F., preferably from about 675 to 720 F. In the lower portion of the temperature range, the reaction can be relatively slow, while in the upper portion of the temperature range, the

5 terials are present, they can constitute from 40 to about extent of coking can become more significant. 95 weight percent of the total catalyst composite. The products from the reaction zone generally include In some instances, the catalysts, either supported or unupgraded liquid products, some gaseous products, and supported, can be associated with sufiicient, though genminor amounts of coke. The gaseous products can include erally minor amounts, of alkali or alkaline earth metals removed sulfur in the form of carbonyl sulfide and/or to minimize or eliminate acid sites which would otherhydrogen sulfide. wise promote cracking side reactions. The following specific examples show the preparation Such solid catalysts can be prepared by any suitable of the specific catalysts of this invention and the method means known in the art. For example, they can be preof using catalysts of this invention in desulfurization, repared by coprecipitation, impregnation, or dry mixing. 5 ducing carbon residues and increasing the API gravity Whichever method of preparation is used, the composiusing liquid feedstock, and liquefying solid hydrocarbon tions should be catalytic in that they will have a surface feedstock. These examples are meant to be illustrative area of at least about 1 square meter per gram. They are and are not exclusive. generally activated prior to use by calcination in air at XAM 800-1500 F. Catalyst regeneration is similarly carried E PLE I out Preparation of barium-treated cobalt molybdate catalyst Presently preferred catalyst systems are those containing molybdenum associated with barium. Particularly A banHFn'tIBatedPObaIt molybdiite catalyst was good results are obtained using a catalyst comprising copared by lmPYegnatm? a cmme,rc1auy available cobalt halt molybdate dispersed on a predominantly alumina molybdate catalyst with a solution of banum acetate. support material and impregnated with Sufiicient barium Specifically, an alumina-supported cobalt molybdate c atsalt solution, such as a solution of barium nitrate or alyst (AER? P11334441 Aniencan Cyanamlde barium acetate or other carboxylic acid barium salt, to .Company) the ,form of an 1/32 i extrudate was provide from about 1 to about 20, preferably from about mlprefgnated m thls manner by sllblectmg f ZOO-gram 2 to about 15, weight percent barium. Another catalyst gummy of the Fatalyst to elm/[act with a Solutlon p which has been found to be particularly effective is an mg.55 of ba.num actitate m 85 water After lmgreg' unsupported barium molybdate catalyst in which the barnatlon j drymg the lmpregnated extrudate P calclnefl ium and molybdenum are present in approximately at 1100 F. for about 4-5 hours. The composit on of this stoichiometric quantities. catalyst, both before and after the incorporation of the The catalysts of the present invention are bifunctional banum shown In the followmg Table in that they have activity for both the water gas shift re- TABLE 1 actlon and hydrogenatlon- [Composition and properties of cobalt molybdate catalyst and its barium The hydrocarbon conversion process of the present inpmnmted denvmves] ventio n is carried out in liquid phase which in this ap- 40 Bat-promoted plication means as a totally liquid mixture or as a slurry molggg tg mol l l i of solid hydrocarbons in a liquid hydrocarbon carrier and y 8 1n the presence of carbon monoxide. The process can be ilggg gifgg flgfi 3g 2g carried out both batchwise, such as in an autoclave, or it Po e di t nn-III: I 71 84 can be carried out continuously such as in a fixed bed glifl gg gg gg'gggg i"? 19%; reactor. Any convenient type of reactor can be used. In o yb u Weight P175551?- any event, suflicient carbon monoxide will be present to 333,521 ;$5"" 3-3 5% provide a reaction pressure in the range of about 1000 t 1 i m to about 5000 psig preferably in the range of about a SSIOH spec rograp ic ana ysis n cated t a presence of trace tn rF,o,M, do. 1500 to about 3500 p.s.1.g. Steam, when used, will be a lc ed al sg an n present in the reaction zone in amounts corresponding to abratio of liquid waterzliquid hydrocarbon feed of from EXAMPLE 2 a out 1:5 to about 1:100 by volume. In batch operations, the ratio of solid catalyst to feedstock will be in the range i ffifggg giggg cggall ggi g g 01 3i? over of about 0.1 to about 20, preferably from about 1 to y ys about 5, weight percent catalyst based upon the weight A 50/50 blend of Eocene and Ratawi crude oils were of the feedstock and the reaction time will generally be in treated according to the Process of the P 686m invention the range of about 0.1 to abount 20 hours. In continuous using the catalyst described in the preceding example. The fixed-bed processes, the liquid hourly space rate of th conversions were carried out in a stirred autoclave for feed Wlll generally be 1n the range of from about 0.2 to five hours under several sets of conditions. The essential about 10 LHSV. details and the results of these tests are shown in Table 2.

TABLE 2 Run number Feed 0 1 2 3 4 5 '0 h Operating conditions:

Temperature, F......:: 675 7 678 708 660 708 egc pgsggiiljj 00 0 /0 00/3 00/0 00 3 00 3 1112333530 2.0 11.3 4.0 7.00 1.0 2.0 API' 00 F. gravity 20.4 31.9 20.0 20.5 18.9 27.7 Carbon, wt. percent--- 83.7 84.3 86.45 85.4 85.4 84.9 84.7 Hydrogen, wt. percent. 11.6 11.2 10.92 11.64 11.9 10.7 12.09 glfihlrnrgvlfioggrlcennnu 4.0 3.4 2.4 2.9 2.5 3.8 2.8 g e ggn t 1 15.0 40.0 27.5 37.0 0.0 32.4 percent.... 9.07 0.70 0.30 11.04 0.32 9.70 0.0

TABLE '2Coniti-nue'd Run number Feed 1 2 3 4 5 6 h Gases, mole percent:

Feed=a 50/50 blend 0! Eocene and Ratawl crudes. b 4.8 percent H added.

The data in the table above show that the process of the invention was successful in substantially decreasing the sulfur content of the feedstock. Further, it is seen that Runs 2-6 using the invention process have, in several crude oils was subjected to the process of the invention utilizing both carbon monoxide and steam in 5-hour autoclave reactions. The essential details and the results of these tests are shown in the following Table 3.

TABLE 3 Run number Feed Hzo erude r i Temperature,

Molecular weight Gas Analysis:

Methane. Ethane/ethylene Propane/propylene Heavi 919999.? :oBeorm-waeerecnc instances, increased the API gravity of the oil as well as reducing its carbon residue value. This was generally ac-, complished with the production of relatively small quantities of coke. The presenceof substantial amounts of car bonyl sulfide in the invention runs indicate that the substantial portion of the sulfur is removed from the crude oil in the form of this compound. In the invention Run 6 in which 4.8% water (based upon the feed) was added, there appears to be a reduction in the amount of coke which was formed. Run 5 indicates that, under these specific conditions, a temperature higher than 660 F. is desirable.

EXAMPLE 3 Conversion of crude oil with carbon monoxide-steam over barium-promoted cobalt molybdate In another series of runs, the same /50 blend of ,The results of these tests show that as much as 40% of the sulfur can be removed at temperatures which are.

EXAMPLE 4 Conversion of coal-oil slurry with CO over bariumpromoted cobalt molybdate catalyst A slurry of powdered coal in anthracene oil was desulfurized according to the process of the present invention in a 5-hour autoclave run at 2200-2275 p.s.i.g. The essential conditions of the run and. the results are shown in the following Table 4.

TABLE 4 Feed composition AAn- Slurry thracene B of A+ oil l coal 5 B e Run Run 11 Weight percent- 86. 3 l3. 7 100 97. 6 93. 3 Benzene insoluble matter, weight percent. Nil 99+ 13. 7 8 63 10. 75 Pyridine insoluble matter, weight percent Nil 99+ 13.7 3. 2 5. 0 Catalyst, weight percent... 0 5 Temperature, F 670 750 Conversion of coal To benzene solnbles, percent 37. 2 21. 5 To pyridine solubles, percent 46. 7 63. 5 Composition and properties:

Carbon, weight percent 90. 6 68. 0 87. 6 89.6 91. 26 Hydrogen, wt. percent..- 6. 1 5. 0 5. 88 5. 9 6. 26 Oxygen, wt. percent-..-- 1. 2 u 11. 28 2. 58 2. 2 1. 7 Nitrogen, wt. percent.. 0.78 1. 0 0.81 0. 73 0.98 Sulfur, wt. percent 0. 69 2. 97 0. 90 0. 61 0. 54 Ash, wt. percent Nil 11. 75 1. 61 1. 56 Carbon residue, percent.. 2. 78 65. 11. 50 10. 89 6. 62 Molecular weight 1 69 Sulfur removal, percent 0 32. 89 40. 0

Anthracene oil contained primarily pheneanthrene. b Washed southern Illinois coal.

v Physical mixture, assuming no reaction:

' Moisture-free basis.

6 By diflerence.

Analyses of the gaseous products from these runs are 30 shown in the following table. The original gas was comprised solely of CO which was used to pressurize the autoclave to 100 p.s.i.g. at about 75 F. at the start of the test.

These data clearly indicate that COS is the primary reaction product. Carbon dioxide can be derived from the reaction of CO with oxygen-containing derivatives of the coal products. H 5 can be formed by hydrogen exchange with the aromatic compounds such as phenanthrene which is a major component in the anthracene oil.

EXAMPLE 5 Liquefaction of coal with CO-steam over bariumpromoted cobalt molybdate catalyst In this example, a slurry of coal (a washed coal obtained from southern Illinois) in anthracene oil was subjected to the process of the present invention in a 5-hour autoclave run. The reaction conditions included the presence of carbon monoxide, steam, and catalyst. The catalyst was the same as that prepared in Example 1. The

essential conditions and results of these runs are shown in Table 5 below.

TABLE 5 Run number Feed 12 13 Operatin conditions:

Coal anthracene oil retio....-.-.-: 1/6. 4 1/6. 3

Water/total hydrocarbon feed 0. 163 0. 17

Catalyst, BaO on lit-4311, wt. percent. 0.0 5. 2

Temperature, F 708 700 Pressure. p s l w 3, 250 3,375 Liquid product:

Total recovery, wt. percent 100.00 95. 0

Benzene insolubles, wt. percent.. 16. 3 5. 4.5 3. 59

Pyridine insolnbies, wt. percent 16. 3 2. 44 1. 75 Conversion of coal:

To benzene sols., percent....- 74. 0

Carbon residue, (Rams) percent-. 10.1

To pyridine sols., percent 87. 4

BIG mol ratio 0. 87

Sulfur, wt. percent 0. 44

I Moisture-free basis.

glCalculated properties oi physical=83.3% anthracene oil and 16.7% co The data in the above table show that the catalytic invention Run 13 converted 74.0% of the coal into benzene soluble matter, in addition to substantially reducing the sulfur content of the coal slurry.

EXAMPLE 6 Liquefaction of coal with (DO-steam using soluble catalysts In a manner closely analogous to that of the preceding example, a similar coal/anthracene oil slurry was converted in a 5-hour autoclave run employing carbon monoxide, steam, and several combinations of oil-soluble metal naphthenates. The essential conditions and results of these runs are shown in Table 6.

' TABLE 6 Run number Feed I 14 15 16 17 Test conditions:

Coal/anthracene oil ratio 1/4.5 1/4 5 1/4 5 1/4. 5

Water/hydrocarbon ratio... 1/5.5 1/5 5 1/5 5 1/5 5 Catalyst (as naphthenates) Ba/Ni Ba/Co Ba/Mo Ba/Fe Catalyst added, wt. percent 4.4/3 6 5.5/3 6 5. 5/3 6 5.5/3 6 Temperature, F 705 71 610 Pressure, p.s.i.g 3, 200 3, 400 3, 400 3, 400 Liquid product:

Total recovery, wt. percent 9S. 6 B 101. 5 98. 5 95. 6

Benzene insolubles, wt. percent. 16. 3 5. 63 5. 49 4.80 5. 67

Pyridine insolubles, wt. percent 16. 3 3.79 2.99 5.4 3.79

a-Hexane insolubles, wt. percenL.-- 16.3 10. 7 12. 5 Conversion of coal rcent:

To benzene soiub es 68. 7 67. 1 65. 3 66.

To pyridine solubles- 77. 1 82. 0 67. 7 77. 4

To hexane solubles 35. 25. 0 13. 6

Carbon residue, percent 13.02 9. 08 8. 49 8.82

ulfur, wt. percent 1.00 0 63 0. 43 0. 53 0.43

I Properties of blend as calculated from composition of ieed used in tests.

As corresponding metal naphthenates. Contains some coke derived from the CO. d Moisture-free basis.

The data above show that the combination of barium naphthenate salts together with nickel, cobalt, molybdenum, or iron naphthenate salts also catalyze the liquefaction of coal in the presence of carbon monoxide.

EXAMPLE 7 Conversion of crude oil with CO-steam over barium molybdate catalyst In this series of runs, a 50/50 mixture of Eocene and Ratawi crude oils were desulfurized according to the process of the present invention using an unsupported barium molybdate (46.2 weight percent Ba) catalyst. The tests were conducted in a 300 C. rocking autoclave equipped with a quartz liner. The crude oil, catalyst, and water, if used, were added to the autoclave which was then closed and flushed several times with nitrogen. After pressuring to 1000 p.s.i.g. with CO at room temperature, heat was applied as rapidly as possible until the desired operating temperature was reached. The tests were of five hours duration. The pressures shown in the table were at the beginning of the reaction period. As water was consumed, pressures were distinctly lower towards the end of the tests.

TABLE 7 25 The data show that, without a catalyst, no substantial Reasonable variation and modification are possible within the scope of the foregoing disclosure and the appended claims to the invention the essence of which is that a heavy hydrocarbon feedstock can be reacted in the presence of carbon monoxide and a catalyst comprising an active metal and an alkaline earth metal at elevated temperatures and pressures to improve the quality of the reactive material.

I claim:

1. A method for desulfurization of heavy liquid hydrocarbon feed stock comprising:

Run number Feed 18 19 20 21 Operating details:

Temperature, F I 708 711 709 728 Pressure, p.s.i.g 2, 200 2, 200 2, 650 4, 100 BaMoO4, wt. percen None 4. 4. 55 4. 0 Metal naphthenate None None None None Weight, percent naphthenate None None None None Water, wt. percent None None 4. 55 16. 0 Coke, wt. percent 7. 2 1. 67 2. 3 2. 33 Liquid product:

Weight, percent 96. 0 96.2 96. 3 API gravity, 60 F- 20.4 26. 0 24. 4 24. 8 23. 7 Carbon, wt. percent..- 83. 7 84. 8 83. 7 84. 3 86. 2 Hydrogen, wt. percent 11. 6 11. 7 11. 7 11.9 10. 7 Sulfur, wt. percent 4. 00 b 3. 6 3. 1 3. 2 2. 8 Sulfur removed, percente 10. 0 24. 4 22. 0 32. 7 Carbon residue, percent- 9. 07 6. 14 8. 17 7. 72 6. 57 Gaseous materials, mol percent:

728 728 a, 900 3, 850 2. 7 2. 7 Co Ni 1. 37 1. 37 13. 7 13. 7 1. 55 3. 0

I IO-hour run. b Converted to yield basis. Based on 3.6 value.

11 (a) passing into a reaction chamber a reactant consisting essentially of carbon monoxide, said reactant present in amounts suflicient to provide a reaction pressure in a range of about 1500 to about 3500 p.s.i.g., and

(b) reacting said hydrocarbon feed stock in the liquid phase with said carbon monoxide reactant in the presence of a catalytically active metal selected from molybdenum, tungsten, nickel, cobalt, copper, iron, and zinc, for a time and at a temperature sufiicient to carry out the process of desulfurization 2. The method of claim 1 wherein said catalytically active metal is associated with analkali metal or an alkaline earth metal.

3. The method of claim 1 wherein said catalytically active metal is associated with a catalytic support selected from the group consisting of alumina, bauxite, Group IIA metal aluminate and mixtures thereof, said support comprising from about 40 to about 95 weight percent of the total catalyst composition.

4. The method of claim 1 wherein said temperature is in the range from about 550 to about 800 F.

5. The method of claim 4 wherein said reaction is carried out batchwise and the ratio of solid catalyst to feedstock is in the range of about 0.1 to about 20 weight percent catalyst based on weight of feedstock and the reaction time is in the range of about 0.1 to about 20 hours.

6. The method of claim 5 wherein steam is present in the reaction zone in a ratioof liquid water to liquid hydrocarbon feed of from about 1:5 to about 1:100 by volume.

7. The method of claim 4 wherein said reaction is continuous in a fixed span and the liquid hourly space velocity of the feed is in the range of about 0.2 to about 10.

8. The method of claim 7 wherein steam is present in the reaction zone in a ratio of liquid water to liquid hydrocarbon feed of from about 1:5 to about 1:100 by volume.

9. The method of claim 3 wherein the catalyst is barium-promoted cobalt molybdate.

References Cited UNITED STATES PATENTS 2,242,387 5/1941 Boyd 208-208 R 2,917,532 12/1959 Watkins 208--209 FOREIGN PATENTS 413,181 2/1966 Japan 208-209 DELBERT E. GANTZ, Primary Examiner G. J. CRASANAKIS, Assistant Examiner US. Cl. X.R.