CA1276578C - Catalytic two-stage coal hydrogenation and hydroconversion process - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

A process for two-stage catalytic hydrogenation and liquefaction of coal to produce increased yields of low-boiling hydrocarbon liquid and gas products. In the process, the particulate coal is slurried with a process-derived liquid solvent and fed at temperature below about 650°F into a first stage catalytic reaction zone operated at conditions which promote controlled rate liquefaction of the coal, while simultaneously hydrogenating the hydrocarbon recycle oils at conditions favouring hydrogenation reactions. The first stage reactor is maintained at 650-800°F temperature, 1000-4000 psig hydrogen partial pressure, and 10-60 lb coal/hr/ft3 reactor space velocity. The partially hydrogenated material from the first stage reaction zone is passed directly to the close-coupled second stage catalytic reaction zone maintained at a temperature at least about 25°F higher than for the first stage reactor and within a range of 750-875°F temperature for further hydrogenation and thermal hydroconversion reactions.
By this process, the coal feed is successively catalytically hydrogenated and hydroconverted at selected conditions, which results in significantly increased yields of desirable low-boiling hydrocarbon liquid products and minimal production of undesirable residuum and unconverted coal and hydrocarbon gases, with use of less energy to obtain the low molecular weight products, while catalyst life is substantially increased.

Description

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CATALYTIC TWO-STAGE COAL HYDROGENATION
AND HYDROCONVERSION PROCESS

B~CKGROUND OF THE INVENTION

This invention pertains to an improved catalytic two-stage coal hydrogenation and hydroconversion process to produce increased yields of low-boiling hydrocarbon distillate liquid products. It pertains particularly to such a process in which the coal feed is rapidly heated and catalytically hydro-genated in a first reaction zone containing an ebullated catalyst bed, and then further hydrogenated and hydrocracked in a close-coupled second catalytic reaction zone at slightly higher temperature conditions to produce increased yields of desirable low-boiling hydrocarbon liquid products while minimizing hydrocarbon gas yields and catalyst deactivation.
In the H-Coal single stage coal liquefaction process, a particulate coal feed is usually slurried in a coal-derived recycle oil and the coal-oil slurry is preheated to a temperature near the reaction temperature and then fed with hydrogen into a catalytic ebullated bed reactor, which operates at relatively high temperatures. In the reactor, a major portion of the coal is liquefied to produce hydrocarbon gas and distillate liquid fractions, but an undesirably large fraction of the coal lique-faction product is residual oil containing preasphaltenes andasphaltene compounds. The preasphaltenes are highly unstable species at elevated temperatures, and can decompose thermally in the presence of hydrogen to form asphaltenes while releasing gaseous hydrocarbons and water, but they can also rearrange, aromatize, and even condense to form char. In the reactor, the asphaltenes break down further to heavy and light distillates, naphtha and gaseous hydrocarbons.
In order to achieve satisfactory hydrocarbon liquid products in single-stage catalytic reaction processes, the reactor must be operated at a relatively high temperature which usually produces retrograde materials and places a limit on the distillate liquid yields which can be achieved. Conventional single-stage catalytic processes for coal liquefaction and hydro-genation are generally disclosed in U.S. Patent Nos. 3,519,555 a ~

~ ~'76S~8 and 3,791,959. In attempts to overcome the deficiencies of single-stage catalytic processes for coal liquefaction and hydrogenation, various two-stage catalytic processes have been proposed, including processes having a thermal first stage reactor as well as catalytic-catalytic processes utilizing low first stage temperatures of only 600-700F. Examples of such coal hydrogenation processes using two stages of catalytic reaction are disclosed by U.S. Patent Nos. 3,679,573; 3,700,584;
4,111,788; 4,350,582; 4,354,920; and 4,358,359.
Although these processes using two stages of coal hydrogenation have generally provided some improvements over a single stage coal liquefaction process, such processes usually produce low quality liquid solvent materials in the reactor and do not provide for the desired hydrogenation and high conversion of the coal feed to produce high yields of desirable low-boiling hydrocarbon liquid products with minimal yields of hydrocarbon gas and heavy residuum fractions. Such improved results have now been achieved by the present two-stage catalytic coal hydrogenation and hydroconversion process.
SUMMARY OF THE INVENTION

The present invention provides an improved process for direct two-stage catalytic hydrogenation, liquefaction and hydroconversion of coal to ~roduce significantly increased yields of desirable low-boiling hydrocarbon distillate liquid products with minimal yields of hydrocarbon gas and high-boiling resid fractions. In the process, a particulate coal such as bituminous, sub-bituminous or lignite and a process-derived recycled hydro-carbon liquid solvent material are mixed together and theresulting flowable coal-oil slurry is hydroqenated and liquefied using two staged direct-coupled ebullated bed catalytic reactors connected in series.
The coal-oil slurry is fed into the first stage back-mixed catalytic reaction zone which is maintained at Si 78 selected moderate temperature and pressure conditions and in the presence of a particulate hydrogenation catalyst which promotes controlled rate liquefaction of the coal, while simultaneously hydrogenating the recycle solvent oils at conditions which favour hydrogenation reactions at temperatures less than about 800F. The first stage reaction zone contains an ebullated bed of a particulate hydrogenation catalyst to hydrogenate the aromatic rings in the particulate coal, recycle solvent and dissolved coal molecules and produce the desired low-boiling hydrocarbon liquid and gaseous materials.
The catalyst used in each stage reactor should be selected from the group consisting of oxides or other compounds of cobalt, iron, molybdenum, nickel, tin, tungsten and mixtures thereof, and other hydrocarbon hydrogenation catalyst metal oxides known in the art, deposited on a porous base or support material selected from the group consisting of alumina, magnesia, silica, titania, and similar materials. Useful catalyst particle sizes can range from about 0.030 to 0.125 inch effective diameter.
The first stage reactor is maintained at conditions of 650-800F temperature, 1000-4000 psig hydrogen partial pressure, and at 10-60 lb coal/hr/ft3 reactor feed rate or space velocity to produce a high quality hydrocarbon solvent materialr while achieving at least about 50 W ~ conversion of the coal to tetrahydrofuran (THF) soluble materials. At such mild reaction conditions, hydrocracking, condensation and polymerization reactions along with formation of hydrocarbon gases are all advantageously minimized. Preferred first-stage reaction conditions are 700-7gO~ temperature; 1500-3500 psig hydrogen partial pressure and a coal space velocity of 15-50 lb coal/hr/ft3 reactor, with the preferred conditions being specific to the type of coal being processed.
From the first stage reaction zone, the total effluent material, containing hydrocarbon gases and liquid fractions, is passed with additional hydrogen directly to the second stage back-mixed catalytic reaction zone where the material is further 7~

hydrogenated and hydrocracked at a temperature at least about 25F higher than for the first stage reaction zone. Both stage reaction zones are upflow, well mi~ed ebullated bed catalytic reactors. For the second stage reactor, operating conditions are maintained at higher severity conditions which promote more complete thermal conversion of the coal to liquids, hydroconversion of primary liquids to distillate products, and product quality improvement via heteroatoms removal at tempera-ture greater than 800F, and with similar hydrogen pressure and a hydroconversion catalyst such as cobalt-moly on alumina support. The desired second stage reaction conditions are 750-875F temperature, 1000-4000 psig hydrogen partial pressure and coal space velocity of 10-60 lb coal/hr/ft3 reactor volume to achieve at least about 90 W % conversion of the remaining reactive coal along with the asphaltene and preasphaltene compounds to lower boiling hydrocarbon materials, and the heteroatoms are further reduced to provide THF soluble product materials. Preferred second stage reaction conditions are 800 860F temperature, 1500-3500 p~ig hydrogen partial pressure, and coal space velocity of 15-50 lb coal/hr/ft3 reactor volume~
This two-stage catalytic coal liquefaction process provides high selectivity to low-boiling hydrocarbon liquid products and desired low yields of Cl-C3 hydrocarbon gases and residuum materials, together with minimal deactivation of the catalyst as measured by residuum conversion, which provides for extended activity and useful life of the catalyst. Overall, the present two-stage catalytic process produces higher yields of distillate and lower molecular weight products which are considerably more paraffinic an~ "~etroleum-like" in terms of their chemical structure, than are produced by other single or two-stage direct coal liquefaction processes. It has been determined that the Watson characterization factor for the hydrocarbon liquid products in relation to their mean average boiling point from the present catalytic two-stage process are intermediate those products produced by the H-Coal~ single-stage catalvtic process and by petroleum catalytic hydroconversion processes.

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The present two-stage direct coal liquefaction process advantageously provides a significant improvement over the single-stage H-Coal~ coal liquefaction process, by providing an integrated recycle solvent hydrogenation step upstream of the conventional catalytic ebullated bed reactor~ The reaction conditions are selected to provide controlled hydrogenation and conversion of the coal to liquid products (as defined by solubility in quinoline, tetrahydrofuran, or other similar solvent), while simultaneously hydrogenating the recycle and coal-derived product oils. Because the coal feed is dissolved in a high quality hydrocarbon solvent in the low temperature first-stage reactor, the potential for retrogressive (coke forming) reactions is significantly reduced and solvent quality, hydrogen utilization and heteroatom removal are appreciably improved, which increases potential conversion of the coal while extending the catalyst life. The high quality effluent slurry material from the first stage reactor is fed to the close-coupled second stage catalytic reactor operated at somewhat higher temperatures to achieve increased coal conversion to mainly distillate liquid products. The process thermal efficiency is advantageously improved over other two-stage coal liquefaction proeesses. Also, because of the high percentage conversion of coal to low-boiling hydrocarbon distillate liquids which is achieved, higher boiling residuum fractions can be recycled to the first stage reactor. Thus, the present process advantageously achieves higher yields of distillate and lower molecular weight hydrocarbon products and less heteroatoms with lower energy input than for single stage catalytic processes, and also for other thermal and thermal/catalytic two-stage coal liquefaction processes.

BRIEF DESCRIPTION OF DRAWINGS

Fig. 1 is a schematic flow diagram of a two-stage catalytic eoal hydrogenation and liquefaction process in aceordance with the invention.

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Fiy. 2 is a graph showing the effect of first stage reactor temperatures on the yield of C4-975F hydrocarbon product liquid.

DESCRIPTION OF THE INVENTION

In the present invention, improved hydrogenation and liquefaction of coal is achieved by a two-stage catalytic process using two well-mixed ebullated bed catalytic reactors direct-connected in series. As is shown in Fig. 1, a coal such as bituminous, sub-bituminous or lignite is provided at 10 and passed through a coal preparation unit 12, where the coal is ground to a desired particle size range such as 50-375 mesh (U.S. Sieve Series) and dried to a desired moisture content such as 3-10 W % moisture. The particulate coal is then slurried in tank 14 with sufEicient process-derived recycle solvent liquid 15 having a normal boiling temperature above about 550F to provide a flowable slurry. The weight ratio of solvent oil/coal is usually 1.4 5.0, with 1.5-3.0 being preferred. The coal/oil slurry is pressurized at pump 16, mixed with recycled hydrogen at 17, preheated at heater 18 to 600-650F temperature and is then fed into the lower end of first stage back-mixed catalytic ebullated bed reactor 20. Fresh make-up high-purity hydrogen is provided as needed at 17a.
The coal-oil slurry and hydrogen streams enter reactor 20 containing an ebullated catalyst bed 22, passing uniformly upwardly through flow distributor 21 at flow rate and at temperature and pressure conditions to accomplish the desired hydrogenation reactions. The operation of the ebullated bed catalytic reactor including internal recycle of reactor liquid upwardly through the expanded catalyst bed at a recycle ratio exceeding about 2:1 is generally well known and is described by U.S. Patent No. 4,437,973, Huibers et al., issued March 20, 1984. The first stage reactor 20 preferably contains a particulate hydrogenation catalyst such as cobalt molybdate, nickel molybdate, or nickel tungsten on an alumina or silica ~ 276~f~3 support material. In addition, fresh particulate hydrogenation catalyst may be added to reactor 20 at connection 23 in the ratio of about 0.1 to 2.0 pounds of catalyst per ton of coal processed. Spent catalyst may be removed at connection 24 to maintain the desired catalytic activity within the reactor.
Operating conditions in the first stage reactor are maintained at a moderate temperature range of 650-800F, 1000-4000 psig hydrogen partial pressure, and coal feed rate or space velocity of 10-60 lb coal/hr/ft3 reactor volume which is equivalent to about 22-132 lb/hr/ft3 catalyst settled volume in the reactor. The preferred reaction conditions of 700-790F
temperature, 1500-3500 psig hydrogen partial pressure and 15-50 lb coal/hr/ft3 reactor volume, or about 33-110 lb/hr/ft3 catalyst settled volume in the reactor, will be specific to the particular coal beinq processed, because different coals convert to liquids under thermal conditions at different rates.
The optimal first stage reaction conditions will allow maximum utilization of hydrogen shuttling solvent compounds, such as pyrene/hydropyrenes, known to be present in coal-derived recycled oils, since catalytic rehydrogenation of donor species occurs simultaneously with solvent-to-coal hydrogen transfer.
Coal-derived oils are also exposed to an efficient catalytic hydrogenation atmosphere immediately upon their formation, reducing the tendency for regressive repolymerization reactions which lead to poor quality hydrocarbon liquid products. First stage reactor thermal severity has been found to be quite important, as too hig~ a severity leads to a coal conversion rate which is too rapid for the catalytic hydrogenation reactions to keep pace, as well as poorer hydrogenation equilibrium for the solvent compounds. Too low a thermal severity in the first stage, while still providing an efficient atmosphere for solvent hydrogenation, does not provide sufficient coal conversion to provide a substantial process improvement.
In the first stage reactor, the objective is to hydrogenate the aromatic rings in molecules of the feed coal, 7~7~3 recycle solvent and dissolved coal so as to produce in situ a high quality hydrogen donor solvent liquid in the presence of hydrogen and the hydrogenation catalyst. At the moderate catalytic reaction conditions used, heteroatoms are removed, retrogressive or coke forming reactions are essentially eliminated, and hydrocarbon gas formations are effectively minimized. Because of the reaction conditions used, i.e., relatively low temperature first stage, the catalyst promotes coal hydrogenation and minimizes polymerization and cracking reactions. Also because of these improved conditions in the first stage reactor, less coke is deposited on the catalyst at the milder reaction conditions used, and the deposited coke also has a desirably higher hydrogen/carbon ratio than for prior processes, which minimizes catalyst deactivation and appreciably prolongs the effective life of the catalyst.
From the first stage reactor 20, the total effluent material at 26 is mixed with additional preheated hydrogen at 27 and flows directly to the lower end of close-coupled second stage catalytic reactor 30. This reactor 30 which operates similarly to reactor 20 contains flow distributor grid 31 and catalyst bed 32, and is operated at a temperature at least about 25F higher than for the first stage reactor, and usually in the temperature range of 750-875F, but at temperatures lower than conventionally used for single-stage catalytic coal liquefaction processes. The higher temperature used in reactor 30 may be accomplished by utilization of the preheated hydrogen stream 28 as well as the second stage reactor heat of reaction. The second stage reactor pressure is slightly lower than for the first stage reactor to permit forward flow of the coal slurry material without any need for pumping, and additional ~akeup hydrogen is added at 29 to the second stage reactor as needed. A particulate catalyst similar to that used in the irst stage reactor is utilized in bed 32 for the second stage reactor.

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g In the second stage reactor 30, the reaction conditions are selected to provide a more complete catalytic conversion of the unconverted coal to liquids, utilizing the-high quality solvent liquid produced in the first stage reactor. I'he remaining reactive coal as well as preasphaltenes and asphaltenes are converted to distillate liquid products along with additional heteroatoms removal. Substantial secondary conversion of coal derived liquids to distillate products, and product upgrading by heteroatoms removal, is also accomplished in the second stage reactor. The reaction conditions are selected to minimize gas formation or dehydrogenation of the first stage liquid effluent materials. Useful reactor conditions are 750-875F
temperature, 1000-4000 psig hydrogen partial pressure, and coal space velocity of 10-60 lb coal/hr/ft3 reactor volume.
Preferred reaction conditions will depend on the particular type coal being processed, and are usually 800-860F temperature, 1500-3500 psig hydrogen partial pressure and 15-50 lb coal/hr/ft3 reactor space velocity.
It is an important characteristic of this process that very little change in the hydrocarbon compounds composition occurs between the first and second stage reactions. It has been found that the 850~F-distillate liquids contain much lower levels of condensed aromatics and are significantly more aliphatic than are products produced from a conventional single stage catalytic coal hydrogenation process. Recycle of residual oil greatly enhances hydrogenation and hydro-conversion of the coal in the first stage reactor.
From the second stage reactor 30, the effluent material at 38 is passed to a phase separator 40 operating at near reactor condition.s, wherein a vapour fraction 41 is separated from a solids-containing liquid slurry fraction at 44. The vapour fraetion 41 is treated at hydrogen purification section 42, from which hydrogen stream 43 is withdrawn for recycle by compressor 43a to the reactors 20 and 30. Fresh make-up hydrogen is added as needed at 17a. A vent gas ,, , ., . .

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containing undesired nitroyen and sulfur compounds is removed from purification section 42 as stream 45.
The slurry liquid fraction 44 is pressure-reduced at 47 to near atmospheric pressure, such as about 200 psig, and passed to a distillation system generally shown at 50.
The resulting liquid fractions are recovered by a vapour/liquid flash in the distillation system 50, including atmospheric and vacuum distillation steps to produce light distillate product stream 51 and a heavier higher-boiling distillate liquid product stream 52. A bottoms stream 55 is passed to a liquid-solids separation step 56, from which unconverted coal and ash solids are removed at 57. The liquid stream 58 having reduced concentration oE solids is recycled by pump 59 as slurrying oil 15. If desired, a reduced solids concentration product liquid stream can be withdrawn at 60.
The recycle slurrying oil stream 58 is prepared by blending a portion of the atmospheric separator bottoms liquid slurry (containing 500F+ distillate, residuum, unreacted coal and ash), the atmospheric fractionation bottoms material (600F+ distillate), and vacuum gas oil. This slurrying liquid stream 58 is then recycled back as stream 15 to the mixing tank 14, where it is mixed with the coal feed to form the flowable slurry feedstream to the first stage reactor.
The recycle oil preparation in liquid-solids separation step 56 can be improved by reducing its solids concentration (a-sh and unconverted coal) by using known solids removal means in separation step 56, such as by use of hydro-clones, centrifuges, filters or solvent deashing techniques, with use of liquid hydroclones usually being preferred.
This invention will be further described and better understood by reference to the following Examples of com-parative operations, which Examples should not be construed as limiting the scope of the invention.

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-- 11. --Several runs were made using the present two-stage catalytic process on Illinois No. 6 coal at the reaction conditions shown in Table 1, i.e., 750F first stage reactor temperature and 825F second stage reactor temperature. From the results provided in Table 1, it is seen that substantially improved results including increased hydrogen efficiency and improved distillate liquid yields were achieved, as compared to results for a single stage cataly-tic coal liquefaction process operating at substantially the second stage reaction conditions. It should be noted that the yields of C4-975F
and 390F-975F materials are both significantly greater for the present two-stage process than for single stage processes.

CATALYTIC TWO-STAGE PROCESS PERFORMANCE
Feed: Illinois No. 6 Coal - 70 U.S. Mesh size Catalyst: First Stage - Amocat lC
Second Stage - Amocat lA Single Stage Average Catalyst Age, Catalytic~2) Lb Dry Coal/Lb Catalyst 216.3 664.3 Process OPERATING CONDITIONS
Temperature, F
First Stage 750 750 Second Stage 825 825 850 Pressure, psig 2506 2515 2500 Dry Coal Space Velocity (ea.stage), Lb Dry/Coal/Hr/Ft3 Catalyst 68 68 68 Total Material Recovery, (Gross) W %97.6 97.31 NORMALIZED YIELD, W % Dry Coal Cl-C3 Gas 5.6 5.9 12.1 C4-390F Liquid -17.9 16.21 21.2 390-500F Liquid 48.6 13.9 12.2¦45.2 500-650F Liquid _16.8 16.8J
650-850F Liquid -11.7}15 7 ~14.6 850-975F Liquid 62.1 4-0 64.0 3.7 390-975F Liquid -46.4 -49.4 32.0 C4-975F Liquid 64.3 65.6 53.2 975F+ Material 4.9 4.6 , .. ... - .~ .
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TABLE 1 (Cont'd) Unconverted Coal Ash 11 11.1 H2O ~ 9.2 9.0 CO+CO2 13.51 0.46 0.3 14.1 NH3 1.2S 1.1 2 _2.6 2.7 Total (100 + H2Reacted) 106.1105.56 PROCESS PERFORMANCE
Coal Conversion, W % M.A.F. 94.3 94.8 94.6 975F+ Conversion, W % M.A.F. 86.9 82.2 72.0 Hydrogen Efficiency 10.5 10.7 9~6 C4-975F, W % M.A.F. 72.3 67.2 Organic Sulfur Removal, W % 98.0 96.6 Nitrogen Removal, W %79.2 66.5 C -975F DISTILLATE Q~ALITY

Gravity, API 25.5 23.7 Sulfur, W % 0.035 0.037 Nitrogen, W % 0.19 0.33 Space velocity expressed in terms of catalyst bed settled volume, equivalent to 34 lb coal/hr per ft 3 reactor volume.
This indicates that relatively little change occurs in chemical structure of the compounds in the second stage reactor compared to ~hose in the first stage, and that significantly more aliphatic type compounds are produced in the two-stage catalytic process.
From the improved results achieved by the present process, it was also unexpectedly found that the 850F minus distillate fraction contained much lower levels of condensed aromatics and are significantly more aliphatic than the similar boiling fractions from a single stage catalytic coal lique-faction p~ocess, as is shown in Table 2, showing the proton distribution of the 850F minus distillate liquid.

'~' Single Stage Two-Stage H-Coal~ Process Catalytic Process First Second Stage Stage Aromatics Condensed 24.8 7.4 8.1 Uncondensed 7.0 7.2 7.6 Totals 31.8 14.6 15.7 Alpha Aliphatics Alkyl 11.8 10.8 10.1 Cyclic 18.2 15.5 14.3 Beta Aliphatics Alkyl 16.6 24.4 25.0 Cyclic 13.5 21.1 20.1 Gamma Aliphatics8.0 13.6 14.8 Totals 68.1 85.4 84.3 Additional runs were made for this two-stage catalytic process on sub-bituminous Wyodak coal. Comparative results with the Illinois No. 6 bituminous coal runs of Example 1 are shown in Table 3.

COMPARATIVE PROCESS PERFORMANCE
-WYODAK(2) ILLINOIS NO. 6 WYODAK(13 H-COAL~
TWO STAGE TWO STAGE SINGLE STAGE
Cl-C3 Gas, W ~ M.A.F. Coal 5-7 7-10 5-13 C4-975F, W ~ M.A.F. Coal 63-68 54-68 47-51 Coal Conversion, W ~ M.A.F.
Coal 94-95 79-92 82-91 Hydrogen Consu~ption 6-7 6-8 5-7 Hydrogen Efficiency 10-11 8-9 7-10 975F+ Conversion 81-87 74-90 69-78 (1) Preliminary Data (2) Run 227-4 and 177-87, H-Coal~ Single Stage Catalytic Process It is noted that percent coal conversion and yield of C4-975F material is somewhat less for Wvodak coal than for the Illinois No. 6 coal. Results for the present two-stage '!''`i`~

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catalytic process compared with the H-Coal~ single stage catalytic process on Wyodak coal are also shown in Table 3.
It is noted that although the percent conversion of the Wyodak sub-bituminous coal is comparable to that for the single stage process, the C4-975F yield and the conversion of the 975F+ material are significantly higher than for the single stage process.

During two-stage catalytic operations on Wyodak sub-bituminous coal, the effect of first stage reactor temperature on hydrogen content of reactor liquids and the solvent quality and on C4-975F liquid yields were investigated.
The first stage reactor temperature was varied between 650F
and 775F with the second reactor stage temperature maintained at 810F and at 45 lb/hr/ft3 catalyst space velocity in each reactor. The results for hydrogen content of the reactor liquid as indicated by hydrogen/carbon ratio are shown in Table 4.

FIRST STAGE HYDROGEN TO CARBON RATIO
REACTOR 650-850F LIQUIDS 850F+ LIQUIDS
TEMP. F FIRST STAGE SECOND STAGE FIRST STAGE SECOND STAGE

650 1.35 0.03 1.32 1.09 0.10 0.99 700 1.36 0.01 1.35 1.11 0.04 1.07 750 1.34 0.04 1.30 1.04 0.06 0.98 775 1.29 0.00 1.29 0.97 0.03 0.94 From these data, it is seen that the hydrogen to carbon ratios are greater for the first than for the second stage reactors at temperatures up to about 750~F and decline at 775F first stage temperature. Also, it is pointed out that these hydrogen/carbon ratios are among the highest reported in the literature for processing Wyodak coal.
The effect of first stage reactor temperature on solvent quality is shown in Table 5.

. , FIRST STAGE
REACTOR COAL CONVERSION, W % M.A.F. COAL~2) TEMP F FIRST STAGE SECOND STAGE
650 64.5 60.0 700 70.4 60.8 750 64.1 47.9 750 64.6 49.7 750tl) 51.6 54.2 775 42.6 46.7 (1) Wet coal feed producing lower H2 partial pressure (2) HRI Solvent Quality Test Conditions Coal - Upper Wyodak Temperature - 750F
Residence Time - 30 Minutes Type Test - Thermal Solvent - Stage 1 - Filtered Liquid Product - Stage 2 - Filtered Atmospheric Still Bottoms Conversion - As measured by solubility of microautoclave product in THF

It is noted that the solvent quality is higher in the first stage reactor up to a first stage reactor temperature of about 750F.
The effect of first stage reactor temperature on C4-975F liquid yields is shown in Fig. 2. It is seen that improved C4-975F yields are obtained for increasing first stage reaction temperature from 650F up to about 750F, and that liquid yields are further increased as the second stage reactor temperature is increased from 810F to 825F. Thus, the improved solvent liquid quality achieved in the first and second stage reactors is indicated by the high hydrogen content of the 650-850F and 850F+ reactor liquid fractions as shown in Table 4 and the coal conversions obtained based on the standard test for solvent quality as shown in Table 5.

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The present two-stage catalytic coal liquefaction process is compared with other two-stage thermal-catalytic 5 coal liquefaction processes, as shown in Table 6.

COMPARISON WITH THERMAL CATALYTIC PROCESSES
KERR-MCGEE
TWO-STAGE HRI THERMAL- THERMAL-CATALYTIC C ALYTIC _ATAL~TIC
Coal <--------Wyodak Clovis Point-------->
Cl-C3 Gas, W ~ 8.1 9.9 12.8 C4-850F Liquid, W % 65.5 52.9 52.6 Coal Conversion, W %
M.A.F. Coal89.3 90.2 92.1 Hydrogen Consumption 8.1 6.6 5.2 Hydrogen Efficiency 8.1 8.5 10.1 975F+ Conversion87.4 76.9 78.6 From this comparison, it is seen that the present catalytic two-stage process provides improved results of reduced Cl-C3 gas yields, increased C4-850F liquid yields, and increased conversion of 975F+ fraction material compared to the other processes.
Although this invention has been described broadly and in terms of certain preferred embodiments thereof, it will be understood that modifications and variation of the process can be made within the spirit and scope of the invention, which is defined by the following claims.

Claims (10)

1. A process for two-stage catalytic hydrogenation of coal to produce increased yields of low-boiling hydrocarbon liquid and gaseous products, comprising:
(a) feeding particulate coal and a hydrocarbon slurrying oil having a normal boiling temperature range above about 550°F at a temperature below about 650°F into a pressurized first stage catalytic reaction zone containing coal-derived liquid and hydrogen and a first stage ebullated bed of particulate hydrogenation catalyst selected from the group consisting of oxides of cobalt, iron, molybdenum, nickel, tin, tungsten and mixtures thereof, deposited on a base or support material selected from the group consisting of alumina, magnesia, silica, and combinations thereof;
(b) passing said coal and hydrogen upwardly through said first stage ebullated bed of particulate hydrogenation catalyst, said bed being maintained at 650-800°F temperature and 1000-4000 psig hydrogen partial pressure and 10-60 lb coal/hr/ft3 space velocity to rapidly heat the coal and catalytically hydrogenate it to produce a partially hydrogenated and hydroconverted coal-derived material;
(c) withdrawing said partially hydrogenated coal-derived material containing gas and liquid fractions from said first stage reaction zone, and passing said material directly to a second stage catalytic reaction zone together with additional hydrogen, said second stage reaction zone being maintained at 750-875°F temperature and 1000-4000 psig hydrogen partial pressure for further reacting and hydrocracking the liquid fraction material therein with minimal dehydro-genation reactions to produce gas and lower boiling hydrocarbon liquid products;
(d) withdrawing from said second stage catalytic reaction zone the hydrocracked material containing gas and liquid fractions, and phase separating said material into separate gas and liquid fractions;

(e) passing said liquid fraction to distillation steps and a liquid-solids separation step, from which a liquid stream normally boiling above about 500°F and containing a reduced concentration of particulate solids is recycled to the coal slurrying step; and (f) recovering hydrocarbon gas and increased yields of low-boiling hydrocarbon liquid products from the process.

2. The process of claim 1, wherein the first stage reaction zone is maintained at 700-790°F temperature, 1500-3500 psig hydrogen partial pressure, and 15-50 lb/hr/ft3 reactor space velocity.

3. The process of claim 1, wherein the second stage reaction zone is maintained at 800-860°F temperature and 1500-3500 psig hydrogen partial pressure.

4. The process of claim 1, wherein the first stage reaction zone contains a particulate hydrogenation catalyst comprising nickel and molybdenum on an alumina support material.

5. The process of claim 1, wherein the second stage reaction zone contains a catalyst comprising cobalt and molybdenum on an alumina support material.

6. The process of claim 1, wherein the hydrogen to carbon ratio for the 650°F+ fraction is greater in the first stage reaction zone than in the second stage reaction zone.

7. The process of claim 1, wherein the coal feed is bituminous type coal.

8. The process of claim 1, wherein the coal feed is sub-bituminous type coal.

9. A process for two-stage catalytic hydrogenation of coal to produce increased yields of low-boiling hydrocarbon liquid and gaseous products, comprising:

(a) mixing particulate bituminous coal with sufficient hydrocarbon liquid having a normal boiling temperature range above about 550°F to provide a flowable slurry and feeding the coal-oil slurry at a temperature below about 650°F directly into a pressurized first stage catalytic reaction zone containing coal-derived liquid and hydrogen and a first stage ebullated bed of particulate hydrogenation catalyst selected from the group consisting of oxides of cobalt, iron, molybdenum, nickel, tin, tungsten and mixtures thereof, deposited on a base or support material selected from the group consisting of alumina, magnesia, silica, and combinations thereof;
(b) passing the coal slurry and hydrogen upwardly through said first stage ebullated bed of particulate hydrogena-tion catalyst, said bed being maintained at 700-790°F
temperature, 1500-3500 psig hydrogen partial pressure, and 15-50 lb/hr/ft3 space velocity to rapidly heat the coal and catalytically hydrogenate it to produce a partially hydro-genated and hydroconverted coal-derived material;
(c) withdrawing said partially hydrogenated coal-derived material containing gas and liquid fractions from the upper part of said first stage reaction zone and passing said material to a second stage catalytic reaction zone together with additional recycle hydrogen, said second stage reaction zone being maintained at 800-860°F temperature and 1500-3500 psig hydrogen partial pressure for further reaction and hydrocracking the liquid fraction therein with minimal dehydro-genation reactions to produce gas and low-boiling hydrocarbon liquid products;
(d) withdrawing from the upper part of said second stage catalytic reaction zone the hydrocracked material containing gas and liquid fractions, and phase separating said material into separate gas and liquid fractions;
(e) passing said liquid fraction to distillation steps and a liquid solids separation step, from which an overhead liquid stream normally boiling above about 550°F and containing a reduced concentration of particulate solids is recycled to the coal slurrying step; and (f) recovering hydrocarbon gas and increased yields of low-boiling hydrocarbon liquid products from the process.

10. The process of claim 1, wherein the yield of C4-975°F hydrocarbon liquid fraction is improved for increased first stage reactor temperature between 650°F and 750°F.