Pyrolysis and hydrogenation process

Claim 2

A continuous process for recovery of liquid hydrocarbon values from a solid carbonaceous material feed comprising the steps of: (a) oxidizing particulate carbon containing residue resulting from pyrolysis of the carbonaceous material in an oxidation zone in the presence of a source of oxygen to produce hot particulate carbon containing residue and a combustion gas; (b) passing carbon containing residue and combustion gas from the oxidation zone to a separation zone and separating in the separation zone hot particulate carbon containing residue from the combustion gas; (c) forming hydrogen gas in a conversion zone by reacting at least a portion of the separated hot particulate carbon containing residue with steam in the substantial absence of unpyrolyzed solid carbonaceous material; (d) simultaneously pyrolyzing the carbonaceous material and hydrogenating pyrolysis products of the carbonaceous material by combining hydrogen gas from the conversion zone, the carbonaceous material feed, and a particulate source of heat including carbon containing residue from the conversion zone in a flash pyrolysis reaction zone having a temperature of from about 600° to about 2000° F., a pressure from ambient up to about 10,000 psig, and a solids residence time less than about 5 seconds to yield a pyrolysis product stream containing as solids, a particulate carbon containing residue of pyrolysis and particulate source of heat, and a vapor mixture comprising volatilized hydrocarbons including middle distillates and unreacted hydrogen gas; (e) separating vapor mixture from carbon containing residue; (f) hydrogenating volatilized hydrocarbons in separated vapor mixture with hydrogen gas of the vapor mixture in the presence of catalyst in a vapor hydrogenation zone; and (g) condensing hydrocarbons including middle distillates from the hydrogenated vapor mixture.

Claim 3

A process as claimed in claim 1 in which the temperature of the pyrolysis reaction zone is from about 600° to about 1400° F.

Claim 4

A process as claimed in claim 1 in which the temperature of the pyrolysis reaction zone is from about 900° to about 1400° F.

Claim 5

A process as claimed in claim 1 in which the solids residence time in the pyrolysis reaction zone is from about 0.5 to about 3 seconds.

Claim 6

A process as claimed in claim 1 including the step of introducing steam to the pyrolysis reaction zone for reacting with carbon containing residue therein to generate additional hydrogen gas to further hydrogenate the volatilized hydrocarbons resulting from the pyrolysis of the carbonaceous material feed.

Claim 7

A process as claimed in claim 1 including the step of introducing a source of hydrogen gas to the vapor hydrogenation zone in addition to the unreacted hydrogen in the vapor mixture.

Claim 8

A process as claimed in claim 6 in which hydrogen gas from the conversion zone is introduced to the vapor hydrogenation zone.

Claim 9

A process as claimed in claim 1 in which the carbonaceous material feed contains sulfur which reacts with hydrogen gas in the pyrolysis reaction zone to yield hydrogen sulfide gas, and comprising the additional step of removing the hydrogen sulfide from the volatilized hydrocarbons hydrogenated in the vapor hydrogenation zone by contacting a stream containing the volatilized hydrocarbons and hydrogen sulfide gas with an absorption solution in which hydrogen sulfide gas is soluble.

Claim 10

A continuous process for recovery of liquid hydrogen values from a coal feed comprising the steps of: (a) at least partially oxidizing particulate char resulting from pyrolysis of the coal feed in an oxidation zone in the presence of a source of oxygen and in the substantial absence of coal to produce hot particulate char and gaseous combustion products of the char; (b) separating the hot particulate char from the gaseous combustion products of the char; (c) forming hydrogen gas in a char conversion zone by reacting at least a portion of the separated hot particulate char with steam; (d) simultaneously pyrolyzing the coal feed and hydrogenating pyrolysis products of the coal by combining hydrogen gas from the char conversion zone, the coal feed and a particulate source of heat including hot particulate char from the char conversion zone in a flash pyrolysis reaction zone having an operating temperature of from about 600° to about 1400° F., a pressure of from ambient up to about 10,000 psig, and a coal residence time of less than about 5 seconds to yield a pyrolysis product stream containing particulate char and a vapor mixture comprising unreacted hydrogen gas and hydrogenated volatilized hydrocarbons including middle distillates; (e) introducing steam to the pyrolysis reaction zone for reacting with the hot particulate char therein to generate additional hydrogen gas to further hydrogenate the volatilized hydrocarbons resulting from the pyrolysis of the coal feed; (f) separating vapor mixture from the char; (g) catalytically hydrogenating volatilized hydrocarbons in the separated vapor mixture with unreacted hydrogen gas of the vapor mixture in a vapor hydrogenation zone; and (h) condensing hydrocarbons including middle distillates from the hydrogenated vapor mixture.

Claim 11

A continuous process for recovery of liquid hydrogen values from a coal feed comprising the steps of: (a) at least partially oxidizing particulate char resulting from pyrolysis of the coal feed in an oxidation zone in the presence of a source of oxygen and in the substantial absence of coal to produce hot particulate char and gaseous combustion products of the char; (b) separating the hot particulate char from the gaseous combustion products of the char; (c) forming hydrogen gas in a char conversion zone by reacting at least a portion of the separated hot particulate char with steam; (d) simultaneously pyrolyzing the coal feed and hydrogenating pyrolysis products of the coal by combining hydrogen gas from the char conversion zone, the coal feed and a particulate source of heat including hot particulate char from the char conversion zone in a flash pyrolysis reaction zone having an operating temperature of from about 600° to about 1400° F., a pressure of from ambient up to about 10,000 psig, and a coal residence time of less than about 5 seconds to yield a pyrolysis product stream containing particulate char and a vapor mixture comprising unreacted hydrogen gas and hydrogenated volatilized hydrocarbons including middle distillates; (e) introducing steam to the pyrolysis reaction zone for reacting with the hot particulate char therein to generate additional hydrogen gas to further hydrogenate the volatilized hydrocarbons resulting from the pyrolysis of the coal feed; (f) separating vapor mixture from the char; (g) catalytically hydrogenating volatilized hydrocarbons in the separated vapor mixture with unreacted hydrogen gas of the vapor mixture in a vapor hydrogenation zone; and (h) condensing hydrocarbons including middle distillates from the hydrogenated vapor mixture.

Claim 12

A process as claimed in claim 9 in which the temperature of the pyrolysis reaction zone is from about 900° to about 1400° F.

Claim 13

A process as claimed in claim 9 in which the pressure in the pyrolysis reaction zone is from about 450 to about 3500 psig.

Claim 14

A process as claimed in claim 9 including the step of introducing a source of hydrogen gas to the vapor hydrogenation zone in addition to the unreacted hydrogen in the vapor mixture.

Claim 15

A process as claimed in claim 12 in which hydrogen gas from the conversion zone is introduced to the vapor hydrogenation zone.

Claim 16

A process as claimed in claim 9 in which the solids residence time in the pyrolysis reaction zone is from about 0.5 to about 3 seconds.

Claim 17

A continuous process for recovery of liquid hydrocarbon values from a particulate agglomerative coal feed comprising the steps of: (a) oxidizing particulate char resulting from pyrolysis of the particulate agglomerative coal feed in an oxidation zone in the presence of a source of oxygen and in the substantial absence of coal to produce hot particulate char and a combustion gas; (b) passing the char and combustion gas from the oxidation zone to a separation zone and separating in the separation zone hot particulate char from the combustion gas; (c) forming hydrogen gas in a conversion zone by reacting at least a portion of the separated hot particulate char with steam; (d) subjecting the particulate agglomerative coal feed to flash pyrolysis by continuously; (i) transporting the particulate agglomerative coal feed contained in a carrier gas which is substantially nondeleteriously reactive with respect to the products of pyrolysis of the particulate agglomerative coal feed to a solids feed inlet of a substantially vertically oriented, descending flow, substantially vertically oriented pyrolysis transport flash pyrolysis reactor having a substantially vertically oriented pyrolysis zone operated at a pyrolysis temperature from about 600° to about 2000° F., a pressure of from about 450 to about 3500 psig, and a solids residence time of less than about 5 seconds; (ii) feeding a particulate source of heat including hot particulate char from the oxidation zone to a substantially vertically oriented chamber surrounding the upper portion of the pyrolysis reactor, the inner peripheral wall of said chamber forming an overflow weir to a vertically oriented mixing section of the vertically oriented descending flow, transport flash pyrolysis reactor, the particulate heat source in said chamber being maintained in a fluidized state by the flow therewith of an aerating gas substantially nondeleteriously reactive with respect to the products of pyrolysis of the particulate agglomerative coal feed; (iii) discharging the particulate source of heat over said weir and downwardly into said mixing section at a rate sufficient to maintain said pyrolysis zone at the pyrolysis temperature; (iv) injecting the particulate agglomerative coal feed and carrier gas from the solids feed inlet into the mixing section to form a resultant turbulent mixture of the particulate source of heat, the particulate agglomerative coal feed and the carrier gas; (v) passing the resulting turbulent mixture downwardly from said mixing section to the pyrolysis zone of said pyrolysis reactor to pyrolyze the particulate agglomerative coal feed in the presence of hydrogen gas from the conversion zone while simultaneously hydrogenating pyrolysis products of the particulate agglomerative coal feed to yield a pyrolysis product stream containing as solids the particulate source of heat and a carbon containing solid residue of pyrolysis of the particulate agglomerative coal feed, and a vapor mixture of carrier gas and pyrolytic vapors comprising unreacted hydrogen gas and hydrogenated volatilized hydrocarbons including middle distillates and unreacted hydrogen gas; separating vapor mixture from the char; and (f) hydrogenating volatilized hydrocarbons in separated vapor mixture with hydrogen gas of the vapor mixture in the presence of a catalyst in a vapor hydrogenation zone; and (e) condensing hydrocarbons including middle distillates from the vapor mixture.

Claim 18

A continuous process for recovery of liquid hydrocarbon values from a particulate agglomerative coal feed comprising the steps of: (a) oxidizing particulate char resulting from pyrolysis of the particulate agglomerative coal feed in an oxidation zone in the presence of a source of oxygen and in the substantial absence of coal to produce hot particulate char and a combustion gas; (b) passing the char and combustion gas from the oxidation zone to a separation zone and separating in the separation zone hot particulate char from the combustion gas; (c) forming hydrogen gas in a conversion zone by reacting at least a portion of the separated hot particulate char with steam; (d) subjecting the particulate agglomerative coal feed to flash pyrolysis by continuously; (i) transporting the particulate agglomerative coal feed contained in a carrier gas which is substantially nondeleteriously reactive with respect to the products of pyrolysis of the particulate agglomerative coal feed to a solids feed inlet of a substantially vertically oriented, descending flow, substantially vertically oriented pyrolysis transport flash pyrolysis reactor having a substantially vertically oriented pyrolysis zone operated at a pyrolysis temperature from about 600° to about 2000° F., a pressure of from about 450 to about 3500 psig, and a solids residence time of less than about 5 seconds; (ii) feeding a particulate source of heat including hot particulate char from the oxidation zone to a substantially vertically oriented chamber surrounding the upper portion of the pyrolysis reactor, the inner peripheral wall of said chamber forming an overflow weir to a vertically oriented mixing section of the vertically oriented descending flow, transport flash pyrolysis reactor, the particulate heat source in said chamber being maintained in a fluidized state by the flow therewith of an aerating gas substantially nondeleteriously reactive with respect to the products of pyrolysis of the particulate agglomerative coal feed; (iii) discharging the particulate source of heat over said weir and downwardly into said mixing section at a rate sufficient to maintain said pyrolysis zone at the pyrolysis temperature; (iv) injecting the particulate agglomerative coal feed and carrier gas from the solids feed inlet into the mixing section to form a resultant turbulent mixture of the particulate source of heat, the particulate agglomerative coal feed and the carrier gas; (v) passing the resulting turbulent mixture downwardly from said mixing section to the pyrolysis zone of said pyrolysis reactor to pyrolyze the particulate agglomerative coal feed in the presence of hydrogen gas from the conversion zone while simultaneously hydrogenating pyrolysis products of the particulate agglomerative coal feed to yield a pyrolysis product stream containing as solids the particulate source of heat and a carbon containing solid residue of pyrolysis of the particulate agglomerative coal feed, and a vapor mixture of carrier gas and pyrolytic vapors comprising unreacted hydrogen gas and hydrogenated volatilized hydrocarbons including middle distillates and unreacted hydrogen gas; separating vapor mixture from the char; and (f) hydrogenating volatilized hydrocarbons in separated vapor mixture with hydrogen gas of the vapor mixture in the presence of a catalyst in a vapor hydrogenation zone; and (e) condensing hydrocarbons including middle distillates from the vapor mixture.

Claim 19

The method of claim 15 including the step of injecting steam into the pyrolysis reaction zone to react with the hot particulate char therein to generate additional hydrogen gas to further hydrogenate the volatilized hydrocarbons resulting from the pyrolysis of the coal feed.

Claim 20

The method of claim 16 including the step of introducing carbon dioxide to the pyrolysis reaction zone.

Claim 21

The method of claim 15 including the step of introducing carbon dioxide to the pyrolysis reaction zone.

Claim 22

The method of claim 15 in which the temperature of the pyrolysis reaction zone is from about 600° to about 1400° F.

Claim 23

The method of claim 15 including the step of introducing a source of hydrogen gas to the vapor hydrogenation zone in addition to the unreacted hydrogen in the vapor mixture.

Claim 24

The method of claim 20 in which hydrogen gas from the conversion zone is introduced to the vapor hydrogenation zone.

Claim 25

The method of claim 15 in which the temperature of the pyrolysis reaction zone is from about 900° to about 1400° F.

Claim 26

A continuous process for recovery of liquid hydrocarbon values from a solid carbonaceous material feed comprising the steps of: (a) oxidizing particulate carbon containing residue resulting from pyrolysis of the carbonaceous material in an oxidation zone in the presence of a source of oxygen to produce hot particulate carbon containing residue and a combustion gas; (b) passing the carbon containing residue and combustion gas from the oxidation zone to a separation zone and separating in the separation zone hot particulate carbon containing residue from the combustion gas; (c) forming hydrogen gas in a conversion zone by reacting at least a portion of the separated hot particulate carbon containing residue with steam in the substantial absence of unpyrolyzed solid carbonaceous material; (d) simultaneously pyrolyzing the carbonaceous material and hydrogenating pyrolysis products of the carbonaceous material by combining hydrogen gas from the conversion zone, the carbonaceous material feed, and a particulate source of heat including carbon containing residue from the conversion zone in a flash pyrolysis reaction zone having a temperature of from about 600° to about 2000° F., a pressure from ambient up to about 10,000 psig, and a solids residence time less than about 5 seconds to yield a pyrolysis product stream containing as solids, a particulate carbon containing residue of pyrolysis and particulate source of heat, and a vapor mixture comprising unreacted hydrogen gas and volatilized hydrocarbons including middle distillates; (e) separating vapor mixture from the solids; (f) catalytically hydrogenating volatilized hydrocarbons in separated vapor mixture with unreacted hydrogen gas of the vapor mixture in a vapor hydrogenation zone; and (g) condensing hydrocarbons including middle distillates from the hydrogenated vapor mixture.

Claim 27

A continuous process for recovery of liquid hydrocarbon values from a solid carbonaceous material feed comprising the steps of: (a) oxidizing particulate carbon containing residue resulting from pyrolysis of the carbonaceous material in an oxidation zone in the presence of a source of oxygen to produce hot particulate carbon containing residue and a combustion gas; (b) passing the carbon containing residue and combustion gas from the oxidation zone to a separation zone and separating in the separation zone hot particulate carbon containing residue from the combustion gas; (c) forming hydrogen gas in a conversion zone by reacting at least a portion of the separated hot particulate carbon containing residue with steam in the substantial absence of unpyrolyzed solid carbonaceous material; (d) simultaneously pyrolyzing the carbonaceous material and hydrogenating pyrolysis products of the carbonaceous material by combining hydrogen gas from the conversion zone, the carbonaceous material feed, and a particulate source of heat including carbon containing residue from the conversion zone in a flash pyrolysis reaction zone having a temperature of from about 600° to about 2000° F., a pressure from ambient up to about 10,000 psig, and a solids residence time less than about 5 seconds to yield a pyrolysis product stream containing as solids, a particulate carbon containing residue of pyrolysis and particulate source of heat, and a vapor mixture comprising unreacted hydrogen gas and volatilized hydrocarbons including middle distillates; (e) separating vapor mixture from the solids; (f) catalytically hydrogenating volatilized hydrocarbons in separated vapor mixture with unreacted hydrogen gas of the vapor mixture in a vapor hydrogenation zone; and (g) condensing hydrocarbons including middle distillates from the hydrogenated vapor mixture.

Claim 28

A process as claimed in claim 23 in which the temperature of the pyrolysis reaction zone is from about 600° to about 1400° F.

Claim 29

A process as claimed in claim 23 in which the temperature of the pyrolysis reaction zone is from about 900° to about 1400° F.

Claim 30

A process as claimed in claim 23 in which the solids residence time in the pyrolysis reaction zone is from about 0.5 to about 3 seconds.

Claim 31

A process as claimed in claim 23 including the step of introducing a source of hydrogen gas to the vapor hydrogenation zone in addition to the unreacted hydrogen in the vapor mixture.

Claim 32

A process as claimed in claim 27 in which hydrogen gas from the conversion zone is introduced to the vapor hydrogenation zone.

Claim 33

A process as claimed in claim 23 in which the carbonaceous material feed contains sulfur which reacts with hydrogen gas in the pyrolysis reaction zone to yield hydrogen sulfide gas, and comprising the additional step of removing the hydrogen sulfide from the volatilized hydrocarbons hydrogenated in the vapor hydrogenation zone by contacting a stream containing the volatilized hydrocarbons and hydrogen sulfide gas with an absorption solution in which hydrogen sulfide gas is soluble.

Claim 34

A continuous process for recovery of liquid hydrocarbon values from carbonaceous material feed comprising the steps of: (a) combining particulate carbon containing residue resulting from pyrolysis of the carbonaceous material feed, steam, and a source of oxygen in an oxidation-conversion zone in the substantial absence of unpyrolyzed carbonaceous material to produce hot particulate carbon containing residue and a combustion gas by at least partial oxidation of carbon in the carbon containing residue while simultaneously producing hydrogen gas by reaction of steam which is introduced into the oxidation-conversion zone with carbon in the carbon containing residue;

Claim 35

A continuous process for recovery of liquid hydrocarbon values from carbonaceous material feed comprising the steps of: (a) combining particulate carbon containing residue resulting from pyrolysis of the carbonaceous material feed, steam, and a source of oxygen in an oxidation-conversion zone in the substantial absence of unpyrolyzed carbonaceous material to produce hot particulate carbon containing residue and a combustion gas by at least partial oxidation of carbon in the carbon containing residue while simultaneously producing hydrogen gas by reaction of steam which is introduced into the oxidation-conversion zone with carbon in the carbon containing residue;

Claim 36

(b) simultaneously pyrolyzing the carbonaceous material and hydrogenating pyrolysis products of the carbonaceous material by combining the carbonaceous material feed, hydrogen gas from the oxidation-conversion zone, and a particulate source of heat including carbon containing residue from the oxidation-conversion zone in a flash pyrolysis reaction zone having a temperature from about 600° to about 2000° F., a pressure from ambient up to about 10,000 psig, and a solids residence time of less than about 5 seconds to yield a pyrolysis product stream containing as solids a particulate carbon containing residue of pyrolysis and particulate source of heat, and a vapor mixture comprising volatilized hydrocarbons including middle distillates; and (c) condensing hydrocarbons including middle distillates from the vapor mixture.

Claim 37

(b) simultaneously pyrolyzing the carbonaceous material and hydrogenating pyrolysis products of the carbonaceous material by combining the carbonaceous material feed, hydrogen gas from the oxidation-conversion zone, and a particulate source of heat including carbon containing residue from the oxidation-conversion zone in a flash pyrolysis reaction zone having a temperature from about 600° to about 2000° F., a pressure from ambient up to about 10,000 psig, and a solids residence time of less than about 5 seconds to yield a pyrolysis product stream containing as solids a particulate carbon containing residue of pyrolysis and particulate source of heat, and a vapor mixture comprising volatilized hydrocarbons including middle distillates; and (c) condensing hydrocarbons including middle distillates from the vapor mixture.

Claim 38

A process as claimed in claim 30 in which the source of oxygen is substantially pure oxygen.

Claim 39

A process as claimed in claim 30 in which the temperature of the pyrolysis reaction zone is from about 600° to about 1400° F.

Claim 40

A process as claimed in claim 30 in which the temperature of the pyrolysis reaction zone is from about 900° to about 1400° F.

Claim 41

A process as claimed in claim 30 in which the solids residence time in the pyrolysis reaction zone is from about 0.5 to about 3 seconds.

Claim 42

A process as claimed in claim 30 in which the vapor mixture comprises unreacted hydrogen gas and including the steps of: separating vapor mixture from carbon containing residue; and catalytically hydrogenating volatilized hydrocarbons in the separated vapor mixture with hydrogen gas of the vapor mixture in the presence of catalyst in a vapor hydrogenation zone.

Claim 43

A process as claimed in claim 35 including the step of introducing a source of hydrogen gas to the vapor hydrogenation zone in addition to the unreacted hydrogen in the vapor mixture.

Claim 44

A process as claimed in claim 36 in which hydrogen gas from the oxidation-conversion zone is introduced to the vapor hydrogenation zone.

Claim 45

A process as claimed in claim 35 in which the carbonaceous material feed contains sulfur which reacts with hydrogen gas in the pyrolysis reaction zone to yield hydrogen sulfide gas, and comprising the additional step of removing the hydrogen sulfide from the volatilized hydrocarbons hydrogenated in the vapor hydrogenation zone by contacting a stream containing the volatilized hydrocarbons and hydrogen sulfide gas with an absorption solution in which hydrogen sulfide gas is soluble.

Claim 46

A process as claimed in claim 36 in which the carbonaceous material feed contains sulfur which reacts with hydrogen gas in the pyrolysis reaction zone to yield hydrogen sulfide gas, and comprising the additional step of removing the hydrogen sulfide from the volatilized hydrocarbons by contacting a stream containing the volatilized hydrocarbons and hydrogen sulfide gas with an absorption solution in which hydrogen sulfide gas is soluble.

Claim 47

The method of claim 30 including the step of introducing steam to the pyrolysis reaction zone to react with carbon containing residue therein to generate additional hydrogen gas to further hydrogenate volatilized hydrocarbons resulting from pyrolysis of carbonaceous material feed.

Claim 48

A continuous process for recovery of liquid hydrocarbon values from a coal feed comprising the steps of: (a) combining particulate char resulting from pyrolysis of the coal feed, steam, and a source of oxygen in an oxidation-conversion zone in the substantial absence of unpyrolyzed coal to produce hot particulate char and a combustion gas by at least partial oxidation of carbon in the particulate char while simultaneously producing hydrogen gas by reaction of steam which is introduced into the oxidation-conversion zone with carbon in the particulate char; (b) simultaneously pyrolyzing the coal feed and hydrogenating pyrolysis products of the coal feed by combining the coal feed, hydrogen gas from the oxidation-conversion zone, and a particulate source of heat including hot particulate char from the oxidation-conversion zone in a flash pyrolysis reaction zone having a temperature from about 600° to about 1400° F., a pressure from ambient up to about 10,000 psig, and a solids residence time of less than about 5 seconds to yield a pyrolysis product stream containing particulate char and a vapor mixture comprising unreacted hydrogen gas and volatilized hydrocarbons including middle distillates; (c) introducing steam to the pyrolysis reaction zone to react with particulate char therein to generate additional hydrogen gas to further hydrogenate the volatilized hydrocarbons resulting from the pyrolysis of the coal feed; (d) separating vapor mixture from the char; (e) catalytically hydrogenating volatilized hydrocarbons in separated vapor mixture with unreacted hydrogen gas of the vapor mixture in a vapor hydrogenation zone; and (f) condensing hydrocarbons including middle distillates from the hydrogenating vapor mixture.

Claim 49

A continuous process for recovery of liquid hydrocarbon values from a coal feed comprising the steps of: (a) combining particulate char resulting from pyrolysis of the coal feed, steam, and a source of oxygen in an oxidation-conversion zone in the substantial absence of unpyrolyzed coal to produce hot particulate char and a combustion gas by at least partial oxidation of carbon in the particulate char while simultaneously producing hydrogen gas by reaction of steam which is introduced into the oxidation-conversion zone with carbon in the particulate char; (b) simultaneously pyrolyzing the coal feed and hydrogenating pyrolysis products of the coal feed by combining the coal feed, hydrogen gas from the oxidation-conversion zone, and a particulate source of heat including hot particulate char from the oxidation-conversion zone in a flash pyrolysis reaction zone having a temperature from about 600° to about 1400° F., a pressure from ambient up to about 10,000 psig, and a solids residence time of less than about 5 seconds to yield a pyrolysis product stream containing particulate char and a vapor mixture comprising unreacted hydrogen gas and volatilized hydrocarbons including middle distillates; (c) introducing steam to the pyrolysis reaction zone to react with particulate char therein to generate additional hydrogen gas to further hydrogenate the volatilized hydrocarbons resulting from the pyrolysis of the coal feed; (d) separating vapor mixture from the char; (e) catalytically hydrogenating volatilized hydrocarbons in separated vapor mixture with unreacted hydrogen gas of the vapor mixture in a vapor hydrogenation zone; and (f) condensing hydrocarbons including middle distillates from the hydrogenating vapor mixture.

Claim 50

A process as claimed in claim 41 in which the source of oxygen is substantially pure oxygen.

Claim 51

A process as claimed in claim 41 in which the temperature of the pyrolysis reaction zone is from about 900° to about 1400° F.

Claim 52

A process as claimed in claim 41 in which the solids residence time in the pyrolysis reaction zone is from about 0.5 to about 3 seconds.

Claim 53

A process as claimed in claim 41 including the step of introducing a source of hydrogen gas to the vapor hydrogenation zone in addition to the unreacted hydrogen in the vapor mixture.

Claim 54

A process as claimed in claim 41 in which hydrogen gas from the oxidation-conversion zone is introduced to the vapor hydrogenation zone.

Claim 55

A process as claimed in claim 45 in which the carbonaceous material feed contains sulfur which reacts with hydrogen gas in the pyrolysis reaction zone to yield hydrogen sulfide gas, and comprising the additional step of removing the hydrogen sulfide from the volatilized hydrocarbons hydrogenated in the vapor hydrogenation zone by contacting a stream containing the volatilized hydrocarbons and hydrogen sulfide gas with an absorption solution in which hydrogen sulfide gas is soluble.

Claim 56

A process as claimed in claim 41 in which the carbonaceous material feed contains sulfur which reacts with hydrogen gas in the pyrolysis reaction zone to yield hydrogen sulfide gas, and comprising the additional step of removing the hydrogen sulfide from the volatilized hydrocarbons by contacting a stream containing the volatilized hydrocarbons and hydrogen sulfide gas with an absorption solution in which hydrogen sulfide gas is soluble.

Claim 57

A continuous process for recovery of liquid hydrocarbon values from particulate agglomerative coal feed comprising the steps of: (a) combining particulate char resulting from pyrolysis of the particulate agglomerative coal feed, steam, and a source of oxygen in an oxidation-conversion zone in the substantial absence of unpyrolyzed coal feed to produce hot particulate char and a combustion gas by at least partial oxidation of carbon in the char while simultaneously producing hydrogen gas by reaction of the steam with carbon in the char; (b) subjecting the particulate agglomerative coal feed to flash pyrolysis by continuously: (i) transporting the particulate agglomerative coal feed contained in a carrier gas which is substantially nondeleteriously reactive with respect to the products of pyrolysis of the particulate agglomerative coal feed to a solids feed inlet of a substantially vertically oriented, descending flow, transport flash pyrolysis reactor having a substantially vertically oriented pyrolysis zone operated at a pyrolysis temperature from about 600° to about 2000° F., a pressure of from about 450 to about 3500 psig, and a solids residence time of less than about 3 seconds; (ii) feeding a particulate source of heat including hot particulate char from the oxidation zone to a substantially vertically oriented chamber surrounding the upper portion of the pyrolysis reactor, the inner peripheral wall of said chamber forming an overflow weir to a vertically oriented mixing section of the vertically oriented, descending flow, transport flash pyrolysis reactor, the particulate heat source in said chamber being maintained in a fluidized state by the flow therewith of an aerating gas substantially nondeleteriously reactive with respect to the products of pyrolysis of the particulate agglomerative coal feed; (iii) discharging the particulate source of heat over said weir and downwardly into said mixing section at a rate sufficient to maintain said pyrolysis zone at the pyrolysis temperature; (iv) injecting the particulate agglomerative coal feed and carrier gas from the solids feed inlet into the mixing section to form a resultant turbulent mixture of the particulate source of heat, the particulate agglomerative coal feed and the carrier gas; (v) passing the resultant turbulent mixture downwardly from said mixing section to the pyrolysis zone of said pyrolysis reactor to pyrolyze the particulate agglomerative coal feed in the presence of hydrogen gas from the conversion zone while simultaneously hydrogenating pyrolysis products of the particulate agglomerative coal feed to yield a pyrolysis product stream containing as solids the particulate source of heat and a carbon containing solid residue of pyrolysis of the particulate agglomerative coal feed, and a vapor mixture of carrier gas and pyrolytic vapors comprising hydrogenated volatilized hydrocarbons including middle distillates; and (e) condensing hydrocarbons including middle distillates from the vapor mixture.

Claim 58

A continuous process for recovery of liquid hydrocarbon values from particulate agglomerative coal feed comprising the steps of: (a) combining particulate char resulting from pyrolysis of the particulate agglomerative coal feed, steam, and a source of oxygen in an oxidation-conversion zone in the substantial absence of unpyrolyzed coal feed to produce hot particulate char and a combustion gas by at least partial oxidation of carbon in the char while simultaneously producing hydrogen gas by reaction of the steam with carbon in the char; (b) subjecting the particulate agglomerative coal feed to flash pyrolysis by continuously: (i) transporting the particulate agglomerative coal feed contained in a carrier gas which is substantially nondeleteriously reactive with respect to the products of pyrolysis of the particulate agglomerative coal feed to a solids feed inlet of a substantially vertically oriented, descending flow, transport flash pyrolysis reactor having a substantially vertically oriented pyrolysis zone operated at a pyrolysis temperature from about 600° to about 2000° F., a pressure of from about 450 to about 3500 psig, and a solids residence time of less than about 3 seconds; (ii) feeding a particulate source of heat including hot particulate char from the oxidation zone to a substantially vertically oriented chamber surrounding the upper portion of the pyrolysis reactor, the inner peripheral wall of said chamber forming an overflow weir to a vertically oriented mixing section of the vertically oriented, descending flow, transport flash pyrolysis reactor, the particulate heat source in said chamber being maintained in a fluidized state by the flow therewith of an aerating gas substantially nondeleteriously reactive with respect to the products of pyrolysis of the particulate agglomerative coal feed; (iii) discharging the particulate source of heat over said weir and downwardly into said mixing section at a rate sufficient to maintain said pyrolysis zone at the pyrolysis temperature; (iv) injecting the particulate agglomerative coal feed and carrier gas from the solids feed inlet into the mixing section to form a resultant turbulent mixture of the particulate source of heat, the particulate agglomerative coal feed and the carrier gas; (v) passing the resultant turbulent mixture downwardly from said mixing section to the pyrolysis zone of said pyrolysis reactor to pyrolyze the particulate agglomerative coal feed in the presence of hydrogen gas from the conversion zone while simultaneously hydrogenating pyrolysis products of the particulate agglomerative coal feed to yield a pyrolysis product stream containing as solids the particulate source of heat and a carbon containing solid residue of pyrolysis of the particulate agglomerative coal feed, and a vapor mixture of carrier gas and pyrolytic vapors comprising hydrogenated volatilized hydrocarbons including middle distillates; and (e) condensing hydrocarbons including middle distillates from the vapor mixture.

Claim 59

A process as claimed in claim 49 including the step of injecting steam to the pyrolysis reaction zone to react with the hot particulate char therein to generate additional hydrogen gas to further hydrogenate the volatilized hydrocarbons resulting from the pyrolysis of the coal feed.

Claim 60

A process as claimed in claim 49 in which the temperature of the pyrolysis reaction zone is from about 600 to about 1400° F.

Claim 61

The method of claim 49 including the steps of: separating vapor mixture from the char; and hydrogenating volatilized hydrocarbons in separated vapor mixture with hydrogen gas of the vapor mixture in the presence of a catalyst in a vapor hydrogenation zone.

Claim 62

A process as claimed in claim 52 including the step of introducing a source of hydrogen gas into the vapor hydrogenation zone in addition to the unreacted hydrogen in the vapor mixture.

Claim 63

A process as claimed in claim 53 in which hydrogen gas from the conversion zone is introduced to the vapor hydrogenation zone.

Claim 64

A process as claimed in claim 49 in which the temperature of the pyrolysis reaction zone is from about 900° to about 1400° F.

Claim 65

A continuous process for recovery of liquid hydrocarbon values from carbonaceous material feed comprising the steps of: (a) combining particulate carbon containing residue resulting from pyrolysis of the carbonaceous material feed, steam, and a source of oxygen in an oxidation-conversion zone in the substantial absence of unpyrolyzed carbonaceous material to produce hot particulate carbon containing residue and a combustion gas by at least partial oxidation of carbon in the carbon containing residue while simultaneously producing hydrogen gas by reaction of the steam with carbon in the carbon containing residue; (b) simultaneously pyrolyzing the carbonaceous material feed and hydrogenating pyrolysis products of the carbonaceous material feed by combining the carbonaceous material feed, hydrogen gas from the oxidation-conversion zone, and a particulate source of heat including carbon containing residue from the oxidation conversion zone in a flash pyrolysis reaction zone having a temperature from about 600° to about 2000° F., a pressure from ambient up to about 10,000 psig, and a solids residence time of less than about 5 seconds to yield a pyrolysis product stream containing as solids a particulate carbon containing residue of pyrolysis of the carbonaceous material feed and particulate source of heat, and a vapor mixture comprising unreacted hydrogen gas and volatilized hydrocarbons including middle distillates; (c) separating vapor mixture from the solids; (d) catalytically hydrogenating volatilized hydrocarbons in separated vapor mixture with unreacted hydrogen gas of the vapor mixture in a vapor hydrogenation zone; and (e) condensing hydrocarbons including middle distillates from the hydrogenated vapor mixture.

Claim 66

A continuous process for recovery of liquid hydrocarbon values from carbonaceous material feed comprising the steps of: (a) combining particulate carbon containing residue resulting from pyrolysis of the carbonaceous material feed, steam, and a source of oxygen in an oxidation-conversion zone in the substantial absence of unpyrolyzed carbonaceous material to produce hot particulate carbon containing residue and a combustion gas by at least partial oxidation of carbon in the carbon containing residue while simultaneously producing hydrogen gas by reaction of the steam with carbon in the carbon containing residue; (b) simultaneously pyrolyzing the carbonaceous material feed and hydrogenating pyrolysis products of the carbonaceous material feed by combining the carbonaceous material feed, hydrogen gas from the oxidation-conversion zone, and a particulate source of heat including carbon containing residue from the oxidation conversion zone in a flash pyrolysis reaction zone having a temperature from about 600° to about 2000° F., a pressure from ambient up to about 10,000 psig, and a solids residence time of less than about 5 seconds to yield a pyrolysis product stream containing as solids a particulate carbon containing residue of pyrolysis of the carbonaceous material feed and particulate source of heat, and a vapor mixture comprising unreacted hydrogen gas and volatilized hydrocarbons including middle distillates; (c) separating vapor mixture from the solids; (d) catalytically hydrogenating volatilized hydrocarbons in separated vapor mixture with unreacted hydrogen gas of the vapor mixture in a vapor hydrogenation zone; and (e) condensing hydrocarbons including middle distillates from the hydrogenated vapor mixture.

Claim 67

A process as claimed in claim 56 in which the temperature of the pyrolysis reaction zone is from about 600° to about 1400° F.

Claim 68

A process as claimed in claim 56 in which the temperature of the pyrolysis reaction zone is from about 900° to about 1400° F.

Claim 69

A process as claimed in claim 56 in which the solids residence time in the pyrolysis reaction zone is from about 0.5 to about 3 seconds.

Claim 70

A process as claimed in claim 56 including the step of introducing a source of hydrogen gas to the vapor hydrogenation zone in addition to the unreacted hydrogen in the vapor mixture.

Claim 71

A process as claimed in claim 57 in which the hydrogen gas from the oxidation-conversion zone is introduced to the vapor hydrogenation zone.

Claim 72

A process as claimed in claim 56 in which the carbonaceous material feed contains sulfur which reacts with hydrogen gas in the pyrolysis reaction zone to yield hydrogen sulfide gas, and comprising the additional step of removing the hydrogen sulfide from the volatilized hydrocarbons hydrogenated in the vapor hydrogenation zone by contacting a stream containing the volatilized hydrocarbons and hydrogen sulfide gas with an absorption solution in which hydrogen sulfide gas is soluble.

Claim 73

A continuous process for recovery of values contained in solid carbonaceous materials which comprises the steps of: (a) providing a feed stream containing a particulate solid carbonaceous material; (b) subjecting the particulate solid carbonaceous material to flash pyrolysis by continuously: (i) transporting the particulate solid carbonaceous material containing feed stream contained in a carrier gas which is substantially nondeleteriously reactive with respect to products of pyrolysis of the particulate solid carbonaceous material to a solids feed inlet of a substantially vertically oriented, descending flow pyrolysis reactor having a substantially vertically oriented pyrolysis zone operated at a pyrolysis temperature of from about 600° to about 2000° F.; (ii) feeding a particulate source of heat at a temperature above the pyrolysis zone temperature to a substantially vertically oriented chamber surrounding the upper portion of the pyrolysis reactor, the chamber having an inner peripheral wall forming an overflow weir to a vertically oriented mixing section of the vertically oriented decending flow pyrolysis reactor, the particulate heat source in said chamber being maintained in a fluidized state by the flow therewith of an aerating gas substantially nondeleteriously reactive with respect to the products of pyrolysis of the particulate solid carbonaceous material; (iii) introducing steam to the annular chamber for forming hydrogen gas in said annular chamber by reacting a portion of said char with at least a portion of said steam; (iv) discharging particulate source of heat and hydrogen gas from the annular chamber over said weir and downwardly into said mixing section at a rate sufficient to maintain said pyrolysis zone at the pyrolysis temperature; (v) injecting the particulate solid carbonaceous material feed stream and carrier gas from the solids feed inlet into the mixing region to form a resultant turbulent mixture of the particulate source of heat, the particulate solid carbonaceous material feed and carrier gas; (vi) passing the resultant turbulent mixture downwardly from said mixing section to the pyrolysis zone of said pyrolysis reactor to pyrolyze the particulate solid carbonaceous material while simultaneously hydrogenating pyrolysis products of the particulate solid carbonaceous material to yield a pyrolysis product stream containing as particulate solids the particulate source of heat and a carbon containing solid residue of pyrolysis of the particulate solid carbonaceous material, and a vapor mixture of carrier gas and pyrolytic vapors comprising hydrogenated volatilized hydrocarbons; (c) passing the pyrolysis product stream from said pyryolysis reactor to a separation zone to separate at least the bulk of the particulate solids from the vapor mixture; and (d) forming the particulate source of heat by combining the separated particulate solids with a source of free oxygen in an amount sufficient to raise the solids to a temperature above the pyrolysis temperature.

Claim 74

A continuous process for recovery of values contained in solid carbonaceous materials which comprises the steps of: (a) providing a feed stream containing a particulate solid carbonaceous material; (b) subjecting the particulate solid carbonaceous material to flash pyrolysis by continuously: (i) transporting the particulate solid carbonaceous material containing feed stream contained in a carrier gas which is substantially nondeleteriously reactive with respect to products of pyrolysis of the particulate solid carbonaceous material to a solids feed inlet of a substantially vertically oriented, descending flow pyrolysis reactor having a substantially vertically oriented pyrolysis zone operated at a pyrolysis temperature of from about 600° to about 2000° F.; (ii) feeding a particulate source of heat at a temperature above the pyrolysis zone temperature to a substantially vertically oriented chamber surrounding the upper portion of the pyrolysis reactor, the chamber having an inner peripheral wall forming an overflow weir to a vertically oriented mixing section of the vertically oriented decending flow pyrolysis reactor, the particulate heat source in said chamber being maintained in a fluidized state by the flow therewith of an aerating gas substantially nondeleteriously reactive with respect to the products of pyrolysis of the particulate solid carbonaceous material; (iii) introducing steam to the annular chamber for forming hydrogen gas in said annular chamber by reacting a portion of said char with at least a portion of said steam; (iv) discharging particulate source of heat and hydrogen gas from the annular chamber over said weir and downwardly into said mixing section at a rate sufficient to maintain said pyrolysis zone at the pyrolysis temperature; (v) injecting the particulate solid carbonaceous material feed stream and carrier gas from the solids feed inlet into the mixing region to form a resultant turbulent mixture of the particulate source of heat, the particulate solid carbonaceous material feed and carrier gas; (vi) passing the resultant turbulent mixture downwardly from said mixing section to the pyrolysis zone of said pyrolysis reactor to pyrolyze the particulate solid carbonaceous material while simultaneously hydrogenating pyrolysis products of the particulate solid carbonaceous material to yield a pyrolysis product stream containing as particulate solids the particulate source of heat and a carbon containing solid residue of pyrolysis of the particulate solid carbonaceous material, and a vapor mixture of carrier gas and pyrolytic vapors comprising hydrogenated volatilized hydrocarbons; (c) passing the pyrolysis product stream from said pyryolysis reactor to a separation zone to separate at least the bulk of the particulate solids from the vapor mixture; and (d) forming the particulate source of heat by combining the separated particulate solids with a source of free oxygen in an amount sufficient to raise the solids to a temperature above the pyrolysis temperature.

Claim 75

A process as claimed in claim 63 in which the pyrolysis temperature is from about 600° to about 1400° F.

Claim 76

A process as claimed in claim 63 in which the pyrolysis temperature is from about 900° to about 1400° F.

Claim 77

A process as claimed in claim 63 in which the vapor mixture comprises unreacted hydrogen gas and including the steps of: separating vapor mixture from carbon containing residue; and hydrogenating volatilized hydrocarbons in separated vapor mixture with hydrogen of the vapor mixture in the presence of catalyst in a vapor hydrogenation zone.

Claim 78

A process as claimed in claim 66 including the step of introducing a source of hydrogen gas to the vapor hydrogenation zone in addition to the unreacted hydrogen in the vapor mixture.