Process for determining presence of mesophase in slurry hydrocracking

Patent metadata

Field	Value
Publication number	US-9732284-B2
Application number	US-201113329874-A
Country	US
Kind code	B2
Filing date	Dec 19, 2011
Priority date	Jun 30, 2008
Publication date	Aug 15, 2017
Grant date	Aug 15, 2017

Abstract

A process and apparatus is disclosed for converting heavy hydrocarbon feed into lighter hydrocarbon products. The heavy hydrocarbon feed is slurried with a catalyst comprising iron oxide and alumina to form a heavy hydrocarbon slurry and hydrocracked to produce lighter hydrocarbons. The slurry hydrocracking reaction can be controlled by measuring the production of mesophase using X-ray diffraction. Upon a mesophase yield fraction reaching a predetermined level, reaction conditions should be moderated to avoid excessive coke production.

First claim

The invention claimed is:

1. A method of operating a SHC reactor comprising:
delivering heavy hydrocarbon feed, hydrogen and catalyst to a SHC reactor;
cracking the feed over catalyst in the presence of hydrogen at predetermined reaction conditions;
taking a sample of material from the SHC reactor;
blending the sample with a solvent;
decanting a liquid phase from the sample;
drying the liquid phase to provide a remaining solids;
mixing the remaining solids with a second solvent to provide a mixture;
evaporating the second solvent from the mixture to provide a TIOR solids,
determining the presence of mesophase insoluble in toluene in the sample by identifying the presence of a peak at 26 two theta degrees plus or minus 0.3 two theta degrees in an XRD plot, wherein the XRD plot is based upon the TIOR solids; and
adjusting the reaction conditions in response at least in part to the determination of the presence of mesophase in the sample.

2. The method of claim 1 further comprising:
determining a fraction of mesophase in the sample;
determining the yield fraction of mesophase as the weight ratio of mesophase produced per hydrocarbon fed to the reactor using the fraction of mesophase in the sample; and
adjusting the reaction conditions in response to a determination that the yield fraction of mesophase is at or above 0.8%.

3. The method of claim 1 further comprising:
scanning at least a portion of the sample with an XRD instrument; and
plotting the data output from the XRD instrument by two theta degrees versus intensity.

4. The method of claim 1 further comprising:
separating solids in the sample from liquid;
dissolving the solids in the sample in the solvent;
separating insoluble solids in the sample from soluble solids; and
scanning the insoluble solids in with an XRD instrument.

5. The method of claim 1 further including:
blending the insoluble solids with a predetermined concentration of a standard material before scanning the sample; and
comparing the area under the peak between about 20 and about 29.5 degrees two theta excluding the peak for the standard on the plot to the area under the peak for the standard to proportionally determine the concentration of mesophase in the sample.

6. The method of claim 1 further including calculating the yield fraction of mesophase produced per weight of hydrocarbon fed to a SHC reactor by using the concentration of mesophase in the sample.

7. The method of claim 3 further including adjusting the reaction conditions to avoid excessive coking if the yield fraction of mesophase is at or above 0.5 wt-%.

8. A method of operating a SHC reactor comprising:
delivering heavy hydrocarbon feed, hydrogen and catalyst to a SHC reactor;
cracking the feed over catalyst in the presence of hydrogen at predetermined reaction conditions;
taking a hydrocarbon material from the SHC reactor;
blending the hydrocarbon material with toluene;
decanting a liquid phase from the hydrocarbon material;
obtaining TIOR solids of the hydrocarbon material to provide a sample of hydrocarbon material by drying the liquid phase to provide a remaining solids;
mixing the remaining solids with a second solvent to provide a mixture;
evaporating the second solvent from the mixture to provide the TIOR solids;

scanning the sample of the hydrocarbon material with an x-ray diffraction (XRD) instrument;
plotting the data output from the XRD instrument by two theta degrees versus intensity, wherein the XRD plot is based upon the TIOR solids;
determining a fraction of mesophase insoluble in toluene in the sample by identifying a peak at 26 two theta degrees plus or minus 0.3 two theta degrees;
determining the yield fraction of mesophase as the weight ratio of mesophase produced per hydrocarbon fed to the reactor using the fraction of mesophase in the sample; and
adjusting the reaction conditions in response to a determination that the yield fraction of mesophase is at or above 0.8%.

9. The method of claim 8 further including drying the solids providing the sample before scanning the sample.

10. The method of claim 8 wherein determining a fraction of mesophase in the sample includes:
adding an internal standard to the sample to obtain a predetermined concentration of standard in the sample; and
determining the concentration of mesophase in the sample of hydrocarbon material by calculating the area under the peak at 26 two theta degrees in the plot and comparing it to the area of the peak for the internal standard to proportionally determine the concentration of mesophase relative to the predetermined concentration of standard.

11. The method of claim 10 wherein the known internal standard peak is silicon.

12. The method of claim 10 wherein the area under the peak at about 26 two theta degrees includes all of the peaks between about 20 and about 29.5 two theta degrees.

13. The method of claim 12 further including the step of excluding areas of peaks associated with known hydrocarbons that are not mesophase from the area under the peak at about 26 degrees two theta.

14. The method of claim 12 further including the step of excluding areas of peaks associated with the standard if it generates a peak within the range between 20 and 29.5 two theta degrees.

15. A method of operating a SHC reactor comprising:
delivering heavy hydrocarbon feed, hydrogen and catalyst to a SHC reactor;
cracking the feed over catalyst in the presence of hydrogen at predetermined reaction conditions;
taking a hydrocarbon material from the SHC reactor;
blending the hydrocarbon material with a solvent;
decanting a liquid phase from the hydrocarbon material;
obtaining the TIOR solids of the hydrocarbon material to provide a sample of hydrocarbon material by drying the liquid phase to provide a remaining solids;
mixing the remaining solids with a second solvent to provide a mixture;
evaporating the second solvent from the mixture to provide the TIOR solids;

scanning a sample of hydrocarbon material blended with a predetermined concentration of a standard material with an x-ray diffraction (XRD) instrument;
plotting the data output from the XRD instrument by two theta degrees versus intensity, wherein the XRD plot is based upon the TIOR solids;
determining the area under the peak at 26 two theta degrees plus or minus 0.3 two theta degrees in the plot; and
comparing the area under the peak at 26 two theta degrees plus or minus 0.3 two theta degrees to a peak for the internal standard in the sample to proportionally determine the concentration of mesophase in the sample;
determining the yield fraction of mesophase insoluble in toluene as the weight ratio of mesophase produced per hydrocarbon fed to the reactor using the concentration of mesophase in the sample; and
adjusting the reaction conditions in response to a determination that the yield fraction of mesophase is at or above 0.8%.

16. The method of claim 15 wherein the area under the peak at about 26 degrees includes all of the peaks between about 20 and about 29.5 two theta degrees.

17. The method of claim 16 further including the step of excluding areas of peaks associated with the standard if it generates a peak within the range between 20 and 29.5 two theta degrees.

18. The method of claim 1 wherein the second solvent comprises acetone.

Assignees

• Mezza Beckay J
• Bhattacharyya Alakananda
• Ringwelski Andrzej Z
• Uop Llc

Inventors

• Mezza Beckay J
• Bhattacharyya Alakananda
• Ringwelski Andrzej Z

Classifications

• C10G47/04

  Oxides · CPC title

• C10G2300/708

  Coking aspect, coke content and composition of deposits · CPC title

• C10G47/26

  suspended in the oil, e.g. slurries · CPC title

• C10G47/36 Primary

  Controlling or regulating · CPC title