Delayed coking process

Abstract

The present invention provides a delayed coking process comprising a step of subjecting a mixed feed comprises residual heavy hydrocarbon feedstock and bio oil obtained from fast pyrolysis of lignocellulosic biomass of one or more of Jatropha, Cashew nut, Karanjia and Neem to a delayed coking process and a system for the delayed coking process.

Claims

1. A delayed coking process comprising a step of subjecting a mixed feed comprising residual heavy hydrocarbon feedstock and bio oil obtained from fast pyrolysis of lignocellulosic biomass of one or more of Jatropha, Cashew nut, Karanjia and Neem to the delayed coking process, wherein the residual heavy hydrocarbon feedstock has Conradson carbon residue content of 22 to 27 wt % and the bio oil has Conradson carbon residue content of 7 to 10 wt %, wherein the mixed feed comprises 97 to 85 wt % of the residual heavy hydrocarbon feedstock and 3 to 15 wt % of the bio oil.

2. The process as claimed in claim 1, wherein the residual heavy hydrocarbon feedstock has boiling point in the range of 400° to 700° C.

3. The process as claimed in claim 1, wherein the bio oil has boiling point in the boiling range of about 200° to 620° C.

4. The process as claimed in claim 1, wherein the lignocellulosic biomass are selected from the group consisting of roots, stems, leaves and seeds or combination thereof.

5. The process as claimed in claim 1, wherein the mixed feed is obtained by: (a) mixing residual heavy hydrocarbon feedstock and bio oil to obtain a mixture; (b) feeding the mixture thus obtained in step (a) to a bottom of a fractionator along with a condensed recycle oil; and (c) withdrawing the mixed feed from the bottom of the fractionator.

6. The process as claimed in claim 1, wherein the mixed feed is obtained by: (a) feeding the residual heavy hydrocarbon feedstock to a bottom of a fractionator along with a condensed recycle oil; (b) withdrawing a bottom fraction from the bottom of the fractionator; and (c) mixing bio oil with the bottom fraction thus obtained in step (b) to obtain the mixed feed.

7. The process as claimed in claim 1, wherein the mixed feed is heated to a coking temperature prior to subjecting the same to delayed coking process.

8. The process as claimed in claim 7, wherein the coking temperature is in the range of 475° to 510° C.

9. The process as claimed in claim 1, wherein the delayed coking process comprises: (a) feeding the mixed feed to a coker drum and providing residence time for allowing thermal cracking of the mixed feed under coking conditions; (b) withdrawing vapours from the coker drum and adding a quench media to the vapours thus withdrawn to obtain effluent vapours; (c) transporting the effluent vapours thus obtained to a fractionator for separation into various products according to desired boiling ranges.

10. The process as claimed in claim 9, wherein the residence time is in the range of 12 to 38 hours.

Description

BRIEF DESCRIPTION OF PROCESS DRAWINGS

(1) The attached figures show various aspects of the process of the present invention.

(2) FIG. 1, illustrates a representative coking process of the present invention.

(3) FIG. 2, illustrates representative coking process of an embodiment of the present invention

(4) FIG. 3, illustrate pilot plant data showing the effect of biooil addition upon coke yields.

(5) FIG. 4, depicts the relationship between biooil addition upon C.sub.5+ and C.sub.4.sup.− gas yields.

(6) FIG. 5, illustrate Thermo Gravimetric Analysis (TGA) with high Conradson Carbon Residue (CCR) Vacuum Residue (VR).

(7) FIG. 6, illustrate Thermo Gravimetric Analysis (TGA) with low Conradson Carbon Residue (CCR) Vacuum Residue (VR).

(8) FIG. 7 illustrate Thermo Gravimetric Analysis (TGA) data comparison with low and high CCR.

DETAILED DESCRIPTION OF INVENTION

(9) While the invention is susceptible to various modifications and alternative forms, specific embodiment thereof will be described in detail below. It should be understood, however that it is not intended to limit the invention to the particular forms disclosed, but on the contrary, the invention is to cover all modifications, equivalents, and alternative falling within the scope of the invention as defined by the appended claims.

(10) The present invention provides as an improved Delayed coking process in which residual hydrocarbon feedstock is passed into a coking zone, wherein an improvement comprises mixing the residual heavy hydrocarbon feedstock with a biooil generated from fast pyrolysis of different sources of lignocellulosic biomass comprising the routes, stems, leaves and seeds of Jatropha, Karanjia, Neem, Cashew nut, wherein the resulting feedstock mixture contains biooil in the range of 3 to 15 percent by weight.

(11) In a more specific instance, the residual heavy hydrocarbon feedstock boils within a range of about 400° C. to 700° C. and the biooil boils within a range of from about 200° C. to 620° C.

(12) This embodiment of present invention potentially provides the greatest upgrade in value of Delayed coking process: (1) increase in liquid yields, while decreasing the coke yields, (2) improving the quality of coker gas oil (3) reducing ‘vapor overcracking’ and associated loss of liquids to lower gases, (4) reducing ‘hotspots’ and/or ‘blowouts’ & associated safety issues and costs, (5) addition of biooil, also reduces the propensity to produce ‘shot coke’ which produces hard and difficult to handle coke particle, (6) Improvement in quality of Naphtha (RON: 70 to 92), (7) Processing high throughput due to lower coke yield.

(13) Accordingly, the present invention provides, an improved Delayed coking process in which residual heavy hydrocarbon feedstock mixed with biooil is processed under coking conditions to reduce coke yield and increase liquid yield wherein,

(14) a. preheated biooil in the boiling range of 200° C. to 620° C. generated from fast pyrolysis of bio mass being mixed with residual heavy hydrocarbon feedstock in the boiling range of 400° C. to 700° C. to form a mixed feed;

(15) b. the mixed feed being fed to the bottom of the fractionator where it combines with condensed recycle and being pumped out;

(16) c. mixed feed exiting the fractionator being passed through a fired heater for heating up to the desired coking temperature;

(17) d. the hot feed mixture being fed into the coke drum and being provided sufficient residence time for thermal cracking under coking conditions;

(18) e. quenching media being added to the vapor line to quench vapors exiting from coke drum, to avoid coke formation in the vapor line;

(19) f. effluent vapors after quenching, being fed into a fractionator for separation into various products according to desired boiling ranges.

(20) According to the Delayed coking process, the yield of coke is lesser than that of conventional Delayed coking process for coking of residual heavy hydrocarbon feedstock in the boiling range of 400° C. to 700° C., by 2.0 to 20 wt %.

(21) According to the Delayed coking process, the yield of valuable gaseous and liquid products is higher than that of conventional Delayed coking process for coking of residual heavy hydrocarbon feedstock in the boiling range of 400° C. to 700° C., by 2.0 to 20.0 wt %.

(22) In one embodiment of the present invention, the biooil is generated from fast pyrolysis of lignocellulosic biomass comprising the routes, stems, leaves and seeds of Jatropha, Karanjia, Neem, Cashew nut, and contains insoluble pyrolytic lignin, aldehydes, carboxylic acids, carbohydrates, phenols, alcohols and ketones in the boiling range of about 200° C. to 620° C.

(23) In another embodiment of the present invention, the residual heavy hydrocarbon feedstock and the biooil are having Conradson carbon residue content of 15 to 27 wt % and 7 to 10 wt % respectively.

(24) In still another embodiment of the present invention, the amount of biooil in the mixed feed being varied from 3 to 15 wt %.

(25) In yet another embodiment of the present invention, the residence time provided for thermal cracking varies from 12 to 38 hours.

(26) According to the present invention, addition of biooil, also reduces the propensity to produce ‘shot coke’.

(27) In one of the embodiment, the present invention provides an improved Delayed coking process in which residual heavy hydrocarbon feedstock mixed with biooil is processed under coking conditions to reduce coke yield and increase liquid yield wherein,

(28) a. residual hydrocarbon feedstock being fed into the bottom of the fractionator where it combines with condensed recycle and being pumped out,

(29) b. preheated biooil in the boiling range of 200° C. to 620° C. generated from fast pyrolysis of bio mass being mixed with residual hydrocarbon feedstock in the boiling range of 400° C. to 700° C. to form a mixed feed,

(30) c. mixed feed being passed through a fired heater for heating up to the desired coking temperature,

(31) d. the hot feed mixture being fed into the coke drum and being provided sufficient residence time for thermal cracking under coking conditions,

(32) e. quenching media being added to the vapor line to quench vapors exiting from coke drum, to avoid coke formation in the vapor line,

(33) f. products after quenching, being fed into a fractionator for separation into various products according to desired boiling ranges.

(34) According to this process, the yield of coke is lesser than that of conventional Delayed coking process for coking of residual heavy hydrocarbon feedstock in the boiling range of 400° C. to 700° C., by 2.0 to 20 wt %.

(35) According to this process, the yield of valuable gaseous and liquid products is higher than that of conventional Delayed coking process for coking of residual heavy hydrocarbon feedstock in the boiling range of 400° C. to 700° C., by 2.0 to 20.0 wt %.

(36) In yet another embodiment of the present invention, biooil is generated from fast pyrolysis of lignocellulosic biomass comprising the routes, stems, leaves and seeds of Jatropha, Karanjia, Neem, Cashew nut, and contains insoluble pyrolytic lignin, aldehydes, carboxylic acids, carbohydrates, phenols, alcohols and ketones in the boiling range of about 200° C. to 620° C.

(37) In still another embodiment of the present invention, the amount of biooil in the mixed feed being varied from 3 to 15 wt %.

(38) In yet another embodiment of the present invention, the residence time provided for thermal cracking varies from 12 to 38 hours.

(39) According to the present invention, addition of biooil, also reduces the propensity to produce ‘shot coke’.

(40) In one embodiment of the present invention, the residual hydrocarbon feedstock and the biooil are having Conradson carbon residue content of 15 to 27 wt % and 7 to 10 wt % respectively.

(41) In FIG. 1, Biomass (1) from different sources is passed into the pyrolysis reactor (2). The products recovered (3) from top reactor (2) are passed through cyclone (4) to separate biooil vapor (6) and char (5). The biooil vapors (6) are passed through the biooil recovery unit (7). The biooil separated from recovery unit (7) via line (8) and pass into fractionator (11), called main column in the refining industry. The bio, passes through line (10) along with hot residual heavy hydrocarbon feedstock (9) is introduced into bottom of the fractionator (11), where it combines with condensed recycle. This mixture (12) is pumped out using fractionator bottom pump(s) (13) through a coker heater (14), where the desired coking temperature (normally between 475° C. and 510° C.) is achieved, causing partial vaporization and mild cracking. A vapor liquid mixture (15) exits the heater and as control valve (16) diverts it to a coking drum (18). Sufficient residence time is provided in the coking drum to allow thermal cracking till completion of coking reactions. The vapor liquid mixture is thermally cracked in the drum to produce lighter hydrocarbons, which vaporize and exit the coke drum. The drum vapor line temperature (20, 21) is the measured parameter used to represent the average drum outlet temperature. Quenching media (eg. Gas oil or slop oil) is typically added to the vapor line to quench vapors to avoid coke formation in the vapor line. When coke drum (18) is sufficiently full of coke, the coking cycle ends and the heater outlet charge is then switched from first drum (18) to a parallel coke drum (19) to initiate its coking cycle, while the filled drum (18) undergoes a series of steps like steaming, water cooling, coke cutting, vapor heating and draining. The liquid (17) drained from the drums are fed to the blow down section. The cracked hydrocarbon vapors are transferred via line (22) to fractionator bottom (11), where they are separated and recovered. Coker heavy gas oil (HGO) (23) and Coker light gas oil (LGO) (24) are drawn off the fractionator at desired boiling temperature ranges. The fractionator overhead stream, wet gas (30) goes to separator (28), where it is separated into gaseous hydrocarbons (29), water (27) and unstabilized naphtha (25). A reflux fraction (26) is returned to the fractionator (11).

(42) In FIG. 2, the preheated residual hydrocarbon feedstock (39) is fed into the fractionator bottom (41), where it combines with the condensed recycle and pumped out from fractionator (42) bottom. Biomass (31) from different sources is passed into the Pyrolysis reactor (32). The products recovered (33) from reactor top are passed through cyclone (35) to separate biooil vapor (36) and char (34). The biooil vapors are passed through the biooil recovery unit (37). The biooil separated (38) from recovery unit is then mixed with the residual heavy hydrocarbon feedstock exiting from the fractionator (42). This mixture (40) is pumped through a coker heater (45), where the desired coking temperature (normally between 475° C. and 510° C.) is achieved, causing partial vaporization and mild cracking A vapor liquid mixture (46) exits the heater and a control valve (47) diverts it to a coking drum (49). Sufficient residence time is provided in the coking drum to allow thermal cracking till completion of coking reactions. The vapor liquid mixture is thermally cracked in the drum to produce lighter hydrocarbons (51, 52), which vaporize and exit the coke drum. The drum vapor line temperature is the measured parameter used to represent the average drum outlet temperature. Quenching media (eg. Gas oil or slop oil) is typically added to the vapor line (53) to quench vapors to avoid coke formation in the vapor line. When coke drum is sufficiently full of coke, the coking cycle ends and the heater outlet charge is then switched from first drum (49) to a parallel coke drum (50) to initiate its coking cycle, while the filled drum (49) undergoes a series of steps like steaming, water cooling, coke cutting, vapor heating and draining. The liquid (48) drained from the drums is fed to the blow down section. The cracked hydrocarbon vapors (53) are transferred to fractionator bottom, where they are separated and recovered. Coker heavy gas oil (HGO) (61) and Coker light gas oil (LGO) (60) are drawn off the fractionator at desired boiling temperature ranges. The fractionator overhead stream, wet gas (54) goes to separator (56), where it is separated into gaseous hydrocarbons (55), water (57) and unstabilized naphtha (59). A reflux fraction (58) is returned to the fractionator (42).

(43) FIG. 3 and FIG. 4 show yields obtained from Delayed coking pilot plant experiments conducted at different composition of biooil added to the residual hydrocarbon feed.

(44) FIG. 5, FIG. 6 and FIG. 7 show Thermo Gravimetric Analysis (TGA) of mixture of Vacuum Residue (VR) feed having different Conradson Carbon Residue (CCR) with bio-oil.

(45) The following non-limiting examples illustrate in details about the invention. However, they are, not intended to be limiting the scope of present invention in any way.

Example

(46) A Delayed coking pilot plant of 8 Kg/h feed rate was used for carrying out the experiments. Four experiments were conducted using commercially available residual heavy hydrocarbon feedstock (Resid feedstock A) and biooil (containing insoluble pyrolytic lignin, aldehydes, carboxylic acids, carbohydrates, phenols, alcohols and ketones). In one experiment 100 percent Resid feedstock was used and in the other three experiments various mixtures of Resid feedstock and biooil were used.

(47) The experiments were performed in a Delayed coker pilot plant. The operating conditions for all the experiments were 495° C. feed furnace outlet line temperature, 14.935 psig coke drum pressure, 1 wt % steam addition to the coker feed and a feed rate maintained at about 8 kg/h. The operation was in semi batch mode. The vapors from the coking drums were recovered as liquid and gas products and no coker product was recycled to the coker drum.

(48) The Delayed coking pilot plant unit was operated on 16 h cycle of which 12 h consisted of feeding the unit and 4 hrs of the cycle consisted of stripping and quenching. The characteristics of typical Resid feedstock and biooil are summarized in Table-I and Table-II respectively. The details of the four experiments are summarized in Table-III and results are plotted in FIG. 3 and FIG. 4.

(49) From the pilot plant data reported in Table-III, it is evident that with addition of 10 wt % biooil in the residual feedstock coke yield reduces by 20 wt % with respect to that with 100 wt % residual feedstock. FIG. 3 indicates that with addition of biooil in residual feedstock, coke yield decreases up to certain extent of biooil addition and increases thereafter. Biooil is a micro emulsion in which continuous phase in an aqueous solution of holocellulose decompositions products that stabilizes the discontinuous phase of pyrolytic lignin macro-molecules through mechanisms such as hydrogen bonding. The instability is believed to result from breakdown of the emulsion. The pyrolytic lignin in biooil is analogous to asphaltenes in hydrocarbon feed. As the pyrolytic lignin increases in the feed, the propensity to coke formation increases resulting in higher coke yields.

(50) The effect of biooil addition in resid feedstock on C.sub.5+ yield and C.sub.4.sup.− yield is plotted in FIG. 4. From FIG. 4, it is seen that with biooil addition there is no change in C.sub.5+ yield up to certain extent of biooil addition and increases sharply thereafter. It is also observed that beyond certain extent of biooil addition, some of the 150° C..sup.+ was converting to coke, which can be also observed in FIG. 3. It is seen that the yield of C.sub.4.sup.− increases with certain extent of biooil addition and decreases thereafter.

(51) TABLE-US-00001 TABLE I Properties of resid feed Resid feed Property Unit Value Conradson Carbon Residue (CCR) Wt % 22.05 Asphaltene Wt % 7.1 Sulfur Wt % 5.18 Na ppm 4 Mg ppm 1 Ni ppm 91 V ppm 146 Fe ppm 10 Paraffins Wt % 43.5 Aromatics Wt % 56.5

(52) TABLE-US-00002 TABLE II Properties of Biooil Biooil Property Unit Value Conradson Carbon Residue (CCR) wt % 9.65 Carbon wt % 64.3 Hydrogen wt % 10.4 Nitrogen wt % 3.9 Sulfur wt % 2.2 Ash wt % 0.05 Heating value Cal/g 7938 Calcium ppm 42 Nickel ppm 1 Initial boiling point ° C. 200 Final boiling point ° C. 620

(53) TABLE-US-00003 TABLE III Operating Conditions and product yields Expt-2 Expt-3 Expt-4 VR: VR: VR: Expt-1 Biooil Biooil Biooil Sample description VR (95:5) (90:10) (87:13) Water, % of total feed 1.2 0.8 1.1 1.3 COT ° C. 495.0 495.0 495.0 495.0 DCD pressure kg/cm.sup.2 1.05 1.05 1.05 1.05 Product Yield Pattern (Basis: fresh feed) H.sub.2 + C.sub.1 + C.sub.2 wt % 3.47 4.79 3.72 2.43 LPG wt % 3.00 4.27 2.85 2.31 C.sub.5-150° C. wt % 6.09 7.52 4.35 4.61 150-350° C. wt % 27.21 28.95 36.59 28.73 350° C..sup.+ wt % 34.48 31.10 31.78 39.14 Gas yield wt % 6.47 9.06 6.57 4.74 Liquid Yield wt % 67.79 67.57 72.72 72.47 Coke Yield wt % 25.74 23.37 20.71 22.79 Δ Coke yield wt % (−) 9.2 (−) 19.5 (−) 11.5

(54) Thermo Gravimetric Analysis (TGA) of mixture of Vacuum Residue (VR) feed having different Conradson Carbon Residue (CCR) with bio-oil has been carried out and comparative results are given in the Tables IV to VI and FIGS. 5 to 7. From these data, it is observed that the effect of bio oil addition has negligible effect in the case of low CCR VR and there is no reduction in coke yield.

(55) TABLE-US-00004 TABLE IV TGA results of high CCR VR (CED-00407) with bio oil Heating rate: 10 deg C./min upto 500 deg C., held for 6 hrs in inert environment Bio oil, Conversion, Coke, wt % Sample No. wt % wt % 0 Vacuum Resid (VR) CED-00407 68.45 31.55 5 VR + Bio oil (95% + 5%) CE-19036 80.71 19.29 10 VR + Bio oil (90% + 10%) CE-19037 81.78 18.22 15 VR + Bio oil (85% + 15%) CE-19038 76.45 23.55

(56) TABLE-US-00005 TABLE V TGA results of low CCR VR (CED-3118) with bio oil Heating rate: 10 deg C./min upto 500 deg C., held for 6 hrs in inert environment Bio oil, Conversion, Coke, wt % Sample No. wt % wt % 0 Vacuum Resid (VR) CED-3118 93.34 6.66 5 VR + Bio oil (95% + 5%) CE-19492 93.03 6.97 10 VR + Bio oil (90% + 10%) CE-19493 93.2 6.8 15 VR + Bio oil (85% + 15%) CE-19494 93.59 6.41

(57) TABLE-US-00006 TABLE VI Properties of high CCR VR (CED-00407 and low CCR VR (CED-3118) Property Unit CED-00407 CED-3118 CCR Wt % 22.05 11/14.71 Asphaltene Wt % 7.1 5.05 Sulfur Wt % 5.18 0.73 Na ppm 4 1 Mg ppm 1 1 Ni ppm 91 41 V ppm 146 15 Fe ppm 10 17 Paraffins Wt % 43.5 38.8 Aromatics Wt % 56.5 61.8