Source: https://patents.justia.com/patent/20150210606
Timestamp: 2019-10-20 20:24:13
Document Index: 172730980

Matched Legal Cases: ['§120', '§119', '§119', 'Application No. 1214122', 'art 4', 'art 186']

US Patent Application for FISCHER-TROPSCH PROCESS Patent Application (Application #20150210606 issued July 30, 2015) - Justia Patents Search
Justia Patents US Patent Application for FISCHER-TROPSCH PROCESS Patent Application (Application #20150210606)
This is a continuation under 35 U.S.C. §120 of U.S. application Ser. No. 13/802,921, filed Mar. 14, 2013. Priority is claimed under 35 U.S.C. §119(e) to U.S. Provisional Application 61/716,772 filed Oct. 22, 2012. Priority is also claimed under 35 U.S.C. §119(d) to United Kingdom Patent Application No. 1214122.2, filed Aug. 7, 2012. These applications are incorporated herein by reference.
FIGS. 7-12 are schematic illustrations of catalysts or catalyst supports that may be used in the process microchannels. The catalyst illustrated in FIG. 7 is in the form of a bed of particulate solids. The catalyst illustrated in FIG. 8 has a flow-by design. The catalyst illustrated in FIG. 9 has a flow-through structure. FIGS. 10-12 are schematic illustrations of fin assemblies that may be used for supporting the catalyst.
The term “surface feature” refers to a depression in a channel wall and/or a projection from a channel wall that disrupts flow within the channel. The surface features may be in the form of circles, spheres, frustrums, oblongs, squares, rectangles, angled rectangles, checks, chevrons, vanes, airfoils, wavy shapes, and the like, and combinations of two or more thereof. The surface features may contain subfeatures where the major walls of the surface features further contain smaller surface features that may take the form of notches, waves, indents, holes, burrs, checks, scallops, and the like. The surface features may have a depth, a width, and for non-circular surface features a length. The surface features may be formed on or in one or more of the interior walls of the process microchannels, heat exchange channels and/or combustion channels used in accordance with the disclosed process. The surface features may be referred to as passive surface features or passive mixing features. The surface features may be used to disrupt flow (for example, disrupt laminar flow streamlines) and create advective flow at an angle to the bulk flow direction.
One or more of the microchannel reactor cores 110 may be housed in vessel 200. Vessel 200 has the construction illustrated in FIG. 2. Referring to FIG. 2, the vessel 200 contains three Fischer-Tropsch microchannel reactor coress 110. Although three microchannel reactor coress are disclosed in the drawings, it will be understood that any desired number of microchannel reactor coress may be positioned in vessel 200. For example, the vessel 200 may contain from 1 to about 100 microchannel reactors 110, or from 1 to about 10, or from 1 to about 3 microchannel reactors 110. The vessel 200 may be a pressurizable vessel. The vessel 220 includes inlets and outlets 112 allowing for the flow of reactants into the microchannel reactors 110, product out of the microchannel reactors 110, and heat exchange fluid into and out of the microchannel reactors.
Q = m . m   a   x - m . m   i   n m . ma   x × 100
The Fischer-Tropsch product may be further processed to form a lubricating base oil or diesel fuel. For example, the product made in the microchannel reactor 110 may be hydrocracked and then subjected to distillation and/or catalytic isomerization to provide a lubricating base oil, diesel fuel, aviation fuel, and the like. The Fischer-Tropsch product may be hydroisomerized using the process disclosed in U.S. Pat. No. 6,103,099 or 6,180,575; hydrocracked and hydroisomerized using the process disclosed in U.S. Pat. No. 4,943,672 or 6,096,940; dewaxed using the process disclosed in U.S. Pat. No. 5,882,505; or hydroisomerized and dewaxed using the process disclosed in U.S. Pat. No. 6,013,171, 6,080,301 or 6,165,949. These patents are incorporated herein by reference for their disclosures of processes for treating Fischer-Tropsch synthesized hydrocarbons and the resulting products made from such processes.
The hydrocracking reaction may be conducted in a hydrocracking microchannel reactor and may involve a reaction between hydrogen and the Fischer-Tropsch product flowing from the microchannel reactor 210, or one or more hydrocarbons separated from the Fischer-Tropsch product (e.g., one or more liquid or wax Fischer-Tropsch hydrocarbons). The Fischer-Tropsch product may comprise one or more long chain hydrocarbons. In the hydrocracking process, a desired diesel fraction, for example, may be increased by cracking a C23+ fraction to mid range carbon numbers of C12 to C22. A wax fraction produced from the Fischer-Tropsch microchannel reactor 110 may be fed to the hydrocracking microchannel reactor with excess hydrogen for a triple phase reaction. Under reaction conditions at elevated temperatures and pressures, a fraction of the liquid feed may convert to a gas phase, while the remaining liquid fraction may flow along the catalyst. In conventional hydrocracking systems, a liquid stream forms. The use of a microchannel reactor for the hydrocracking reaction enables unique advantages on a number of fronts. These may include kinetics, pressure drop, heat transfer, and mass transfer.
The solution or suspension may contain at least one primary catalyst metal precursor, such as one of the above cobalt-containing precursors or a mixture of cobalt-containing precursors, and at least one secondary catalyst metal precursor. Such secondary catalyst metal precursor(s) may be present to provide a promoter and/or modifier in the catalyst. Suitable secondary catalyst metals may include noble metals, such as Pd, Pt, Rh, Ru, Ir, Au, Ag and Os, transition metals, such as Zr, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo, Tc, Cd, Hf, Ta, W, Re, Hg and Ti and the 4f-block lanthanides, such as La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and/or Lu.
The deactivation rate of the catalyst may thus be such that it can be used in a Fischer-Tropsch synthesis for e.g. more than about 300 hours, or more than about 3,000 hours, or more than about 12,000 hours, or more than about 15,000 hours, all before a catalyst regeneration is required.
The FT-IR spectra may be corrected by subtracting a spectrum for silica. Therefore, the band at 980 cm−1 may appear, in these corrected spectra, as a dip. The “FT-IT intensity ratio” may be calculated using the observed intensities of the 980 cm−1 and 950 cm−1 bands in the corrected spectra, with the intensity of the band maximum at 950 cm−1 being divided by the intensity of the band minimum at 980 cm−1.
f  ( R ) = 1 R  2  π   ln  ( 1 + c )   - [ l   n  ( R R O  1 + c ) ] 2 2  l   n  ( 1 + c )   where   c = σ 2 R O 2 Equation   1
wherein fmode is the frequency at the mode of the lognormal distribution, RO is the numeric average particle radius, and y is an empirical value based on experimental observation. The value of y is determined via comparison of the stability of a selection of catalysts (at least about 5 to 10) with substantially similar compositions but small variations in Co3O4 particle size and size distribution width. These variations may be achieved via minor modifications of the synthesis method e.g. increasing the dilution of the impregnation solution (which is shown in an example to cause subtle changes to the particle size distribution). FTS stability data on these catalysts under the same testing conditions is then collected. Within this set of similar catalysts, y is then manually adjusted to create a spread of D-values such that catalysts which are FTS stable can be distinguished from catalysts which are not stable. For the catalyst composition 42% Co-0.2% Re-0.03% Pt on 16% TiO2/SiO2, the y value is 1.15.
The Co3O4 particle size distribution may influence catalyst FTS activity and stability, such that, preferably, the D-value of the lognormal particle size distribution of Co3O4 particles is about 19 or more. A D-value of 19.2 corresponds to a size distribution with a c-value of about 0.31 and numerical average particle diameter of about 10 nm. A D-value of 19.8 corresponds to a size distribution with a c-value of about 0.31 and an average particle size of about 8 nm. In either of these cases, a decrease in c (e.g. narrowing of the size distribution) would result in an increase in D. Therefore the specification of c≦0.31 over the average particle size range 8-10 nm corresponds to particle distributions defined by having D-values greater than or equal to about 19.
Silica (180-300 μm) 84 g Citric acid monohydrate 25 g
Titanium (IV) bis(ammoniumlactate)dihydroxide 118 g (97 mL) solution (TALH)
Approximate solution volume 130-135 mL
The silica bare catalyst support material is dried at 100° C. for 2 hours and allowed to cool to room temperature before impregnation. 25 g citric acid are dissolved in minimum water at 40 to 45° C. and cooled down to less than 30° C. The citric acid solution is then added to 118 g (97 ml) of titanium (IV) bis(ammoniumlactate)dihydroxide solution (TALH) and made up to the required volume of impregnation, which is about 130 to 135 ml, with water. The required amount of silica (84 g, weight determined after drying) is impregnated by spraying with the resulting citric acid-TALH impregnation solution.
TABLE 1 Support Co(NO3)2 Co(NO3)2 Citic Perrhenic Solution wt 6H2O 6H2O Co3O4 Co acid acid % Re H2O volume Mass Step (g) (g) (Purity 98%) (g) (g) (g) (g) (g) (g) (ml) (ml) (g) % Co
Reaction performance is determined by characterizing the outlet stream; the dry tailgas composition was analyzed using an Agilent 3000A micro gas chromatograph and the outlet flow was measured using a gas meter. The outlet flow of any species is calculated by multiplying the mole percent by the total gas flow, standardized to the same reference condition used for the mass flow controller calibration. The performance of the reactor is judged by conversion of CO and selectivity to methane (plus other hydrocarbon species, up to C8). The amount of CO converted is determined by subtracting the outlet CO flow from the calibrated inlet flow. Conversion percent is calculated by dividing the amount of CO converted by the amount of CO delivered to the reactor inlet. The methane (C1) selectivity is calculated by dividing the amount of methane produced by the amount of CO converted.
Species mole percent in the tailgas, measured by microGC: [species], e.g. [CO]
Total tailgas outlet flow: flowout
CO conversion=100%×(COin−COout)/COin
TABLE 2 Long Term Operation Data
Once 1 Stage Once 1 Stage 1 Stage 1 Stage Through w/recycle Through w/recycle w/recycle w/recycle TOS Range - Start 4.2 30.0 51.0 68.4 109.9 145.1 - End 20.5 46.7 60.4 107.4 142.3 182.4 Duration (days) 16.3 16.7 9.4 39.0 32.4 37.2 Days Since - Regen — — 11.5 58.5 93.4 133.5 Temperature (C.) 205.6 205.0 199.0 201.0 203.5 208.0 Pressure (psig) 350.0 350.0 350.0 350.0 420.0 350.0 DP (psid) 43.6 34.0 39.2 36.7 35.1 34.1 GHSV 15652 11249 13846 11612 12856 11613 CO Prod (v/v/hr) 3165 1949 2780 1971 2239 2275 C5+ Prod (g/g/hr) 1.53 0.97 1.36 0.99 1.11 1.13 Feed Inerts 16.50 35.00 16.50 35.00 35.00 27.00 Feed H2/CO 2.00 1.85 2.00 1.85 1.85 1.79 Tail Gas H2/CO 1.73 1.05 1.70 1.12 1.08 0.90 Reactor Outlet H2O/H2 1.54 3.00 1.52 2.60 2.97 3.31 Reactor Outlet H2O PP (bar) 7.49 6.04 7.56 5.82 7.33 7.31 CO Conv (per pass)* 72.64% 75.96% 72.12% 74.42% 76.35% 74.86% CO2 Select 0.22% 0.33% 0.17% 0.24% 0.26% 0.31% C1 Select 8.02% 6.32% 7.19% 5.95% 6.22% 6.30% C2 Select 0.67% 0.55% 0.61% 0.49% 0.53% 0.61% C3 Select 1.96% 1.73% 2.06% 1.66% 1.75% 1.85% C4 Select 2.33% 2.00% 2.27% 1.95% 2.03% 2.11% C5+ Select (by diff) 86.81% 89.07% 87.70% 89.71% 89.21% 88.83% C5+ Select (by Mat Bal) 88.72% 89.48% 89.17% 88.46% Alpha 0.915 0.930 0.921 0.915 Deactivation Rate (%/day) −0.092% −0.097% −0.063% −0.072%
1 Stage 1 Stage 1 Stage 1 Stage 1 Stage w/recycle w/recycle w/recycle w/recycle w/recycle ** ** TOS Range - Start 186.9 227.1 242.2 291.8 311.1 - End 224.6 236.4 285.3 310.6 320.2 Duration (days) 37.6 9.3 43.0 18.8 9.1 Days Since - Regen 175.7 187.5 236.4 261.7 271.3 Temperature (C.) 209.5 202.0 205.0 224.9 217.0 Pressure (psig) 350.0 419.4 420.0 350.0 350.0 DP (psid) 35.2 22.6 22.8 29.4 19.9 GHSV 11612 9000 9000 11612 8001 CO Prod (v/v/hr) 2002 1748 1730 2099 1473 C5+ Prod (g/g/hr) 0.98 0.88 0.86 0.88 0.68 Feed Inerts 35.00 28.00 28.00 28.00 28.00 Feed H2/CO 1.85 1.79 1.79 1.79 1.79 Tail Gas H2/CO 1.02 0.88 0.74 0.72 0.64 Reactor Outlet H2O/H2 3.02 3.43 3.97 6.15 7.80 Reactor Outlet H2O PP (bar) 5.98 9.02 9.02 6.43 6.94 CO Conv (per pass)* 75.60% 75.26% 74.46% 82.05% 83.55% CO2 Select 0.32% 0.22% 0.30% 1.58% 1.21% C1 Select 7.28% 5.24% 5.81% 14.43% 10.04% C2 Select 0.67% 0.51% 0.51% 0.51% 0.51% C3 Select 1.86% 1.91% 1.91% 1.91% 1.91% C4 Select 2.30% 2.11% 2.11% 2.11% 2.11% C5+ Select (by diff) 87.57% 90.02% 89.16% 75.37% 82.43% C5+ Select (by Mat Bal) 87.16% Alpha 0.898 Deactivation Rate (%/day) −0.080% −0.119% −0.075% −0.076% −0.117% *Simulated Single Stage With Recycle Gas Compositions Based on 74% per pass, 91-92% overall (fresh feed) CO conversion ** Last 2 columns Simulated Single Stage With Recycle Gas Compositions Based on 80% per pass, 95% overall (fresh feed) CO conversion
flowing a reactant mixture in a microchannel reactor in contact with a catalyst to form a product comprising at least one higher molecular weight hydrocarbon product, the microchannel reactor comprising at least one process microchannel and at least one heat exchange channel in thermal contact with the at least one process microchannel, the catalyst being in the at least one process microchannel, the at least one heat exchange channel having a heat exchange fluid in it exchanging heat with the at least one process microchannel;
wherein the conversion of CO from the fresh synthesis gas in the reactant mixture is at least about 70%, and the deactivation rate of the catalyst is less than about 1.4% per day; and
2. The process of claim 1 wherein the catalyst is derived from a catalyst precursor comprising cobalt, a cobalt oxide, or a mixture thereof.
3. The process of claim 2 wherein the catalyst precursor further comprises a support.
4. The process of claim 3 wherein the support comprises a surface modified support wherein the surface modified support comprises a support which is modified by being treated with titania, zirconia, magnesia, chromia, alumina, or a mixture of two or more thereof.
5. The process of claim 3 wherein the support comprises a refractory metal oxide, carbide, carbon, nitride, or a mixture of two or more thereof.
6. The process of claim 3 wherein the support comprises alumina, zirconia, silica, titania, or a mixture of two or more thereof.
7. The process of claim 3 wherein the support comprises silica and its surface is modified by being treated with titania.
8. The process of claim 3 wherein the surface of the support is amorphous.
9. The process of claim 2 wherein the cobalt oxide comprises Co3O4 and/or CoO.
10. The process of claim 4 wherein the surface of the surface modified support is such that neutralization requires at least about 0.2 μmol NH3 per square meter.
11. The process of claim 3 wherein the support for the catalyst precursor has a FT-IR band intensity at about 950:980 cm−1 of at least about 1.2.
12. The process of claim 9 wherein the Co3O4 is in the form of particulates, the numerical average particle diameter of the Co3O4 being less than about 12 nanometers as determined by XRD.
13. The process of claim 2 wherein the catalyst precursor further comprises a noble metal.
18. The process of claim 1 wherein the at least one process microchannel has an internal dimension of width or height of up to about 10 mm.
19. The process of claim 1 wherein the at least one process microchannel has a length of up to about 10 meters.
21. The process of claim 1 wherein the reactant mixture flows in the at least one process microchannel and contacts surface features in the process microchannel, the contacting of the surface features imparting a disruptive flow to the reactant mixture.
29. The process of claim 1 wherein the at least one process microchannel has at least one heat transfer wall and the heat flux for heat exchange within the microchannel reactor is in the range from about 0.01 to about 500 watts per square centimeter of surface area of the at least one heat transfer wall.
30. The process of claim 1 wherein the pressure within the at least one process microchannel is in the range up to about 50 atmospheres.
31. The process of claim 1 wherein the temperature in the at least one process microchannel is in the range from about 150 to about 300° C.
32. The process of claim 1 wherein the contact time of the reactant mixture with the catalyst within the at least one process microchannel is up to about 2000 milliseconds.
33. The process of claim 1 wherein the at least one higher molecular weight hydrocarbon product comprises one or more hydrocarbons boiling at a temperature of at least about 30° C. at atmospheric pressure.
34. The process of claim 1 wherein the at least one higher molecular weight hydrocarbon product comprises one or more hydrocarbons boiling above a temperature of about 175° C. at atmospheric pressure.
35. The process of claim 1 wherein the at least one higher molecular weight hydrocarbon product comprises one or more paraffins and/or one or more olefins of 2 to about 200 carbon atoms.
36. The process of claim 1 wherein the at least one higher molecular weight hydrocarbon product comprises one or more olefins, one or more normal paraffins, one or more isoparaffins, or a mixture of two or more thereof.
37. The process of claim 1 wherein the at least one higher molecular weight hydrocarbon product is further processed using separation, fractionation, hydrocracking, hydroisomerizing, dewaxing, or a combination of two or more thereof.
38. The process of claim 1 wherein the at least one higher molecular weight hydrocarbon product is further processed to form an oil of lubricating viscosity or a middle distillate fuel.
39. The process of claim 1 wherein the at least one higher molecular weight hydrocarbon product is further processed to form a fuel.
40. The process of claim 1 wherein the process microchannel has fluid flowing in it in one direction, the at least one heat exchange channel has fluid flow in a direction that is co-current or counter-current to the flow of fluid in the at least one process microchannel.
41. The process of claim 1 wherein the at least one process microchannel has fluid flowing in it in one direction, the at least one heat exchange channel has fluid flowing in it in a direction that is cross-current to the flow of fluid in the at least one process microchannel.
53. The process of claim 1 wherein the product further comprises H2O and H2, the H2O partial pressure for the product being in the range from about 3 to about 10 bar, the H2O/H2 molar ratio for the product being in the range from about 1:1 to about 5:1.
54. The process of claim 2 wherein the catalyst precursor comprises from about 10% to about 60% by weight cobalt based on the weight of the metal as a percentage of the total weight of the catalyst precursor.
55. The process of claim 2 wherein the catalyst precursor comprises from about 35% to about 60% by weight cobalt based on the weight of the metal as a percentage of the total weight of the catalyst precursor.
56. A process for conducting a Fischer-Tropsch reaction, comprising:
flowing a reactant mixture in a microchannel reactor in contact with a catalyst to form a product comprising at least one higher molecular weight hydrocarbon product, the microchannel reactor comprising at least one process microchannel and at least one heat exchange channel in thermal contact with the at least one process microchannel, the catalyst being in the at least one process microchannel, the at least one heat exchange channel having a heat exchange fluid in it exchanging heat with the at least one process microchannel, the temperature in the at least one process microchannel being in the range from about 175° C. to about 225° C.;
57. A process for conducting a Fischer-Tropsch reaction, comprising:
flowing a reactant mixture in a microchannel reactor in contact with a catalyst to form a product comprising at least one higher molecular weight hydrocarbon product, the microchannel reactor comprising at least one process microchannel and at least one heat exchange channel in thermal contact with the at least one process microchannel, the catalyst being in the at least one process microchannel, the at least one heat exchange channel having a heat exchange fluid in it exchanging heat with the at least one process microchannel, the heat flux for heat exchange in the microchannel reactor being in the range from about 0.2 to about 5 W/cm2;
58. A process for conducting a Fischer-Tropsch reaction, comprising:
flowing a reactant mixture in a microchannel reactor in contact with a catalyst to form a product comprising at least one higher molecular weight hydrocarbon product, the microchannel reactor comprising at least one process microchannel and at least one heat exchange channel in thermal contact with the at least one process microchannel, the catalyst being in the at least one process microchannel, the length of the at least one process microchannel being in the range from about 0.2 to about 3 meters, the at least one heat exchange channel having a heat exchange fluid in it exchanging heat with the at least one process microchannel;
59. A process for conducting a Fischer-Tropsch reaction, comprising:
the reactant mixture comprising H2 and CO, the mole ratio of H2 to CO in the reactant mixture based on the concentration of CO in the fresh synthesis gas being in the range from about 1.4:1 to about 2.1:1, the contact time of the reactant mixture with the catalyst being in the range from 20 to about 500 milliseconds;
60. A process for conducting a Fischer-Tropsch reaction, comprising:
the reactant mixture comprising H2 and CO, the mole ratio of H2 to CO in the reactant mixture based on the concentration of CO in the fresh synthesis gas being in the range from about 1.4:1 to about 2.1:1, the contact time of the reactant mixture with the catalyst being in the range from about 20 to about 500 milliseconds;
61. A process for conducting a Fischer-Tropsch reaction, comprising:
flowing a reactant mixture in a microchannel reactor in contact with a catalyst to form a product comprising at least one higher molecular weight hydrocarbon product, the microchannel reactor comprising at least one process microchannel and at least one heat exchange channel in thermal contact with the at least one process microchannel, the catalyst being in the at least one process microchannel, the length of the at least one process microchannel being in the range from about 0.2 to about 3 meters, the at least one heat exchange channel having a heat exchange fluid in it exchanging heat with the at least one process microchannel, the heat flux for heat exchange in the microchannel reactor being in the range from about 0.2 to about 5 W/cm2;
62. A process for conducting a Fischer-Tropsch reaction, comprising:
wherein the conversion of CO from the fresh synthesis gas in the reactant mixture is at least about 70%, and the gas hourly space velocity for the flow of fluid in the at least one process microchannel being in the range from about 1000 to about 20,000 hr−1; and
Publication number: 20150210606
Patent Grant number: 9359271
Inventors: Stephen Claude LeViness (Columbus, OH), Francis Daly (Waldoboro, ME), Laura Amanda Richard (Abingdon), Sreekala Rugmini (Kerala)
Application Number: 14/680,399