Process for reduction of sulfur in FCC liquid products through the use of carbon monoxide as a reducing agent

Abstract

Disclosed herein is an improved fluidized catalytic cracking process for converting normally liquid hydrocarbon feedstock with simultaneous reduction of sulfur content in the liquid products obtained therefrom which comprises carrying out the cracking process in the presence of carbon monoxide gas as a reducing agent. The process optionally includes a step of premixing the hydrocarbon feedstock with carbon monoxide gas causing major sulfur reduction before effecting the cracking. The premixing is done in a specified nozzle assembly linked to the FCC unit.

Claims

1. A fluidized catalytic cracking process for converting normally liquid hydrocarbon feedstock with simultaneous reduction of sulfur content in the liquid products obtained therefrom comprising carrying out the cracking process in the presence of a reducing agent consisting of carbon monoxide gas wherein the process comprises of premixing the hydrocarbon feedstock with the carbon monoxide gas before effecting the cracking process.

2. The process as claimed in claim 1, comprising introducing preheated hydrocarbon feedstock along with carbon monoxide gas into a primary mixing chamber of a feed nozzle assembly, sweeping the mixture into a secondary mixing chamber of the said nozzle assembly where steam is introduced as a diluent medium to take the mixture preferably into a riser reactor of an FCC unit while simultaneously, passing an upflowing suspension of hot regenerated active fluidized catalyst in a lift gas into the reactor through bottom of a vertically oriented riser reactor at a temperature and residence time sufficient to effect the cracking and to obtain desired liquid products with reduced sulfur content.

3. The process as claimed in claim 2, wherein the hydrocarbon feedstock is introduced into the primary mixing chamber of the nozzle assembly through multiple entry points at an angle of about 90 for intimate mixing with carbon monoxide.

4. The process as claimed in claim 2, wherein the catalyst contains Al.sub.2O.sub.3 in the range of 30-50 wt %.

5. The process as claimed in claim 2, wherein the catalyst contains Re.sub.2O.sub.3 in the range of 1-4 wt %.

6. The process as claimed in claim 2, wherein carbon monoxide gas is used as the lift gas in the riser reactor.

7. The process as claimed in claim 2, wherein the velocity of the lift gas for upflowing the suspension of hot regenerated active fluidized catalyst into the riser reactor is at about 1.5 to less than 15 m/s and catalyst residence time is from about 1.0 to 10 sec.

8. The process as claimed in claim 2, wherein the catalyst used is steamed FCC catalyst.

9. The process as claimed in claim 1, wherein the proportion of carbon monoxide gas used in the process is between about 0.5 to 10 mole % of the feedstock.

10. The process as claimed in claim 1, wherein the feedstock contains sulfur in the range of 0.5 to 5 wt % of the feedstock.

11. The process as claimed in claim 1, wherein the feedstock contains Conradson Carbon Residue (CCR) in the range of 0.1 to 1 wt % of the feedstock.

12. The process as claimed in claim 1, wherein the reduction of sulfur in total liquid products is about 50% and above.

13. The process as claimed in claim 1, wherein the proportion of carbon monoxide gas used in the process is between about 0.5 to 5 mol % of the feedstock.

Description

DESCRIPTION OF THE INVENTION

(1) An improved catalytic cracking process has now been developed which is capable of improving the reduction of the sulfur content in the liquid products of the cracking process.

(2) Being a well-known reducing agent carbon monoxide (CO) is used for removing sulfur in this invention. The reducing nature of CO and its oxidation to COS leads to a reduction of sulfur in the liquid products.

(3) According to this invention there is provided an improved fluidized catalytic cracking (FCC) process for converting sulfur containing normally liquid hydrocarbon feedstock with simultaneous reduction of sulfur content in the liquid products obtained therefrom comprising carrying out the cracking process in the presence of carbon monoxide gas as a reducing agent

(4) The invented process can be worked in any known FCC unit where carbon monoxide (CO) is added to the fluidized cracking catalyst in the riser reactor of the FCC unit where preheated hydrocarbon feed is broken down into lighter hydrocarbon products while reduction of sulfur content in the products takes place simultaneously.

(5) In a preferred embodiment of the invention before bringing the cracking catalyst into contact with the hydrocarbon feedstock for cracking, an intimate atomised mixture of the hydrocarbon feedstock with carbon monoxide reducing agent is separately made and the mixture is then transported to the riser reactor for the desired conversion. Advantage of prior mixing with atomization of the hydrocarbon feed with carbon monoxide is to accomplish major reduction of sulfur from the feed before the cracking process in the riser reactor where conversion of the hydrocarbon feed into lighter liquid hydrocarbon products takes place with further removal of sulfur therefrom.

(6) For commercial application, prior mixture and atomization of the hydrocarbon feed with carbon monoxide is accomplished with the help of a feed nozzle assembly having essentially a primary mixing chamber in flow connected with a secondary mixing chamber as shown in the FIGURE of the accompanying drawing. The schematic design of the said feed nozzle assembly is a subject matter of applicant's pending Indian patent application no 2721/DEL/2009 (PCT application no. WO2011080754).

(7) The feed nozzle assembly of the FIGURE includes at least one primary mixing chamber (PMC) to receive a liquid hydrocarbon feed and a diluent for producing a primary mixture. A secondary mixing chamber (SMC) is flow connected to the primary mixing chamber to receive the primary mixture. In addition, the secondary mixing chamber extends to a tertiary mixture chamber (TMC). Further, a steam inlet is provided to inject streams of steam to the secondary mixing chamber and to the tertiary mixing chamber through a first opening and a second opening, respectively, located within the steam inlet.

(8) The liquid hydrocarbon feedstock is mixed with carbon monoxide (CO) into the primary mixing chamber PMC of the nozzle assembly where intimate mixing of the feedstock takes place with CO. The mixture is then made to be swept into the secondary mixing chamber SMC of the said nozzle assembly where preferably steam being introduced as a diluent to atomize the feed and to take the total mixture preferably into the riser reactor of a FCC unit (not shown) while simultaneously a suspension of hot regenerated active fluidized catalyst is passed in an upflowing manner with the help of a lift gas through lower portion of vertically oriented riser reactor at a temperature and pressure sufficient to effect the cracking and to obtain the desired liquid products with reduced sulfur content. In another embodiment the hydrocarbon feed stock is introduced into the primary mixing chamber of the said nozzle assembly through multiple entry points at an angle of about 90 for intimate mixing with carbon monoxide gas.

(9) According to this invention the proportion of carbon monoxide gas used in the process is between about 0.5 to 10 mole percent of the feedstock, preferably about 0.5 to 5 mole % of the feedstock. The feedstock contains sulfur in the range of 0.5 to 5 wt % of the feedstock and Conradson Carbon Residue (CCR) in the range of 0.1 to 1.0 wt % of the feedstock. The FCC catalyst used can be selected from the conventional ones used in the art. It is preferable that the catalyst contains Al.sub.2O.sub.3 in the range of 30 to 50 wt % and Re.sub.2O.sub.3 in the range of 1 to 4 wt %. The catalyst used is preferably steamed catalyst. The extent of sulfur removal from the liquid products is about 50% and above. The lift gas used in the riser reactor for upflowing the catalyst includes carbon monoxide and the gas velocity is at about 1.5 to less than 15 m/s and the catalyst residence time is from about 1.0 to 10 seconds.

(10) To perform the experiments in micro level, the MAT unit can be used with a modification for separately feeding the feed and CO to the reactor. A cylindrical split furnace is used along with the reactor to achieve the required reaction temperature.

Experimental Results

(11) The base experiment was conducted where 0 mole % CO and 100 mole % fresh feed was used and this is considered to be the base case. For this example the process of the present invention was used as a first run followed by three runs in which CO added in a composition of 5 mole %, 7.5 mole % and 10 mole % along with the fresh feed. The typical physico-chemical properties of catalyst and feedstock are reported in Table-1 and Table-2 respectively.

(12) Table-3 shows the data for those three runs including relevant operating conditions used in the base case. The feedstock for all the runs was high sulfur vacuum gas oil (HS-VGO). For the purpose of comparison, base case run with the identical operating conditions, that was obtained using no CO and a feedstock and conditions, where applicable, identical to the succeeding three runs.

(13) The data in table-3 shows the distribution of yields and sulfur into the products of interest using CO having no other components into it as impurities. The results show that there is an increase in gasoline yield with a decrease in dry gas, FIN and LCO whereby LPG and coke yield remaining more or less constant. Furthermore, with the use of the CO the reduction of sulfur in gasoline up to 31% and in TCO (Total Cycle Oil) up to 45% is quite pronounced. The reduction of sulfur in liquid products has been observed to be more than 50%. We believe that the yields of heavy naphtha and light cycle oil obtained by the practice of the present invention could be improved without significantly increasing coke or dry gas make, by further optimization of the process.

(14) The experimental results, which are based on the experiments and understanding of the conventional FCC process through many years of experience in the FCC art indicate a marked reduction of sulfur in the products through the use of CO.

Characterization of Catalyst and Feed

(15) The selected feedstock and catalyst were characterized using appropriate characterization techniques and results of the characterization of catalyst and feedstock are tabulated in Table-1 and Table-2 respectively.

(16) TABLE-US-00001 TABLE 1 Physico-Chemical Properties of Catalyst Surface Area, m.sup.2/gm Fresh 277 Steamed** 189 Pore Volume, cc/gm 0.355 Crystallinity, wt % Fresh 23.4 Steamed** 17.5 UCS, A Fresh 24.68 Steamed** 24.43 Chemical Analysis, wt % Al.sub.2O.sub.3, 43.18 Re.sub.2O.sub.3 3.47 Fe <0.01 PO.sub.4 <2.0 Attrition Index 3.846 Loss on Ignition, wt % 8.66 Particle Size Distribution, wt % 120 97 105 93 80 71 60 42 40 18 20 4 APS, microns 65.44 ABD, gm/cc 0.910 **Steamed at 788 C./3 hrs

(17) TABLE-US-00002 TABLE 2 Properties of Feed Density @ 15 C., gm/cc 0.9249 Sulfur, wt % 2.5 CCR 0.26 SARA, wt % Saturates 55.5 Aromatics 44.0 Asphaltene 0.5 H.sub.2 Content 12.7 Total N.sub.2, ppm 895 Distillation, D1160 IBP 292 10 352 20 376 30 394 40 411 50 427 60 441 70 456 80 473 90 496 95 512 FBP 540 Metals Nickel <100 ppb Vanadium 150 ppb Sodium <100 ppb Iron 1005 ppb Arsenic <200 ppb Lead 205 ppb Copper <100 ppb Silicon <100 ppb

Characterization of Liquid and Gaseous Products

(18) Liquid products collected were analyzed in Simulated Distillation (SimDist) analyzer for distillation analysis, in N-S analyzer for sulfur distribution analysis and in XRF for total sulfur analysis whereas the gaseous products were analyzed in High Speed Refinery Gas Analyzer (HSRGA). Experimental results are summarized in Table-3.

(19) TABLE-US-00003 TABLE 3 Yield and sulfur distribution in products Base + Base + Base + Base 5.0% CO 7.5% CO 10% CO Normalized Yield H.sub.2 0.05 0.034 0.032 0.03 Dry Gas 2.47 1.28 1.32 1.35 LPG 17.42 17.15 17.40 17.55 Gasoline 30.81 32.27 32.94 33.2 HN 13.02 12.39 11.09 11.21 LCO 24.23 23.436 22.908 22.18 TCO 37.25 35.826 34.60 33.39 Bottoms 7.93 8.9 9.14 9.38 Coke 4.07 4.54 4.92 5.1 Conv, 216 67.84 67.66 67.70 68.44 % reduction of sulfur in 53.02 50.87 48.70 Liquid Products % reduction of sulfur in 31.10 28.80 26.49 Gasoline % reduction of sulfur in 45.00 42.00 38.00 TCO

(20) The embodiments of the invention disclosed herein are only illustrative. There can be several other possible embodiments of the invention also fall within the scope of this invention as would be apparent from the practice of the invention. The full scope and spirit of the invention should be derived from the following appended claims.