Processes and systems for characterizing and blending refinery feedstocks

• US 9,347,009 B2
• Filed: 12/20/2011
• Issued: 05/24/2016
• Est. Priority Date: 12/28/2010
• Status: Active Grant

• Current Assignee: Chevron USA Incorporated (Chevron Corp.)
• Original Assignee: Chevron USA Incorporated (Chevron Corp.)
• Inventors: Kusinski, Grzegorz Jan, Devine, Thomas M.
• Primary Examiner(s): Soderquist, Arlen
• Application Number:
  US13/331,155
• Publication Number:
  US 20120160736A1
• Time in Patent Office: 1,617 Days
• Field of Search: 436/6, 436 60- 61, 436/129, 436/150
• US Class Current: 1/1
• CPC Class Codes: C10L 1/04 essentially based on blends of hydrocarbons
• CPC Class Codes: G01N 33/2876 Total acid number

Abstract

A method for characterizing and optimizing refinery feedstock blends according to their corrosivity is provided. Refinery feedstocks can be characterized based on any of: dissociation of acids in the crude, breakup of naphthenic acid molecular associations, mass changes of carbon steel samples, and/or dissociation of sulfur compounds in the feedstocks. The characterization is performed as a function of temperature via any of electrical resistivity measurement, vibrational spectroscopic analysis, voltammetry, electrochemical impedance spectroscopy, crystal microbalance measurements of weight changes, and combinations thereof. The method employs models and/or hardware to optimize the usage of refinery feedstocks in the blending and valuation of the feedstocks.

Claims

1. A method for optimizing blends of refinery feedstock, comprising:

providing a plurality of refinery feedstock samples with each feedstock sample being representative of a feedstock stream to the refinery and having a molecular association characteristic as a function of temperature;

obtaining measurements from the refinery feedstock samples to quantify the molecular association characteristic of the samples as a function of temperature by electrochemical impedance spectroscopy (EIS) at 10 kHZ frequency;

providing a database containing EIS measurements correlating molecular association characteristics of the refinery feedstock samples as a function of temperature with known corrosion performance of a plurality of reference refinery feedstock samples;

using the EIS measurements correlating molecular association characteristics of the refinery feedstock samples and the database containing EIS measurements correlating molecular association characteristics with corrosion performance of the reference refinery feedstock samples to obtain an optimized feedstock blend having desired EIS measurements correlating with an acceptable corrosion performance.

2. The method of claim 1, wherein the molecular association characteristic is any of molecular break-up of acids, dissociation of acids and/or acidic species, dissociation of sulfur compounds in feedstock samples into ionic species, and combinations thereof.

3. The method of claim 1, further comprising blending the feedstock streams to the refinery in different proportions to obtain the optimized feedstock blend.

4. The method of claim 1, wherein the EIS measurements from the refinery feedstock samples are obtained over a temperature range from ambient to 700°

F.

5. The method of claim 4, wherein the feedstock samples are enriched with water and/or steam at a concentration from 2 ppm to 2 wt. %.

6. The method of claim 1, wherein the EIS measurements from the refinery feedstock samples are obtained under vacuum simulating vacuum distillation conditions.

7. The method of claim 1, wherein the EIS measurements are obtained over a temperature range of ambient to 700°

F. and wherein the feedstock samples are enriched with oxygen at a concentration from I0 to 500 ppm 0₂.

8. The method of claim 1, wherein the EIS measurements are obtained using a two-electrode chemical cell with an ultramicroelectrode as working electrode and a second electrode serving as both reference electrode and counter electrode.

9. The method of claim 1, wherein the EIS measurements detect electrical resistivity changes using a four-point probe housed in a holder that is chemically inert in refinery feedstock.

10. The method of claim 1, wherein the EIS measurements detect electrical resistivity changes using a two-point probe housed in a holder that is chemically inert in the refinery feedstock.

11. The method of claim 1, wherein the refinery feedstock streams are selected from crude oil, synthetic crude, biocrude, refined products, intermediate products such as residue, gas oil, vacuum gas oil, naphtha or cracked stock, and blends thereof.

12. A method for optimizing blends of refinery feedstock, comprising:

providing a plurality of refinery feedstock samples with each feedstock sample being representative of a feedstock stream to the refinery;

obtaining spectroscopic measurements using electrochemical impedance spectroscopy (EIS) at 10 kHz frequency as a function of temperature for the plurality of refinery feedstock samples;

blending the feedstock samples in pre-determined proportions to form a feedstock blend;

obtaining EIS measurements as a function of temperature for the feedstock blend;

comparing the EIS measurements of the feedstock blend to a pre-determined EIS measurements; and

adjusting the proportions of the feedstock samples so that the EIS measurements of the feedstock blend are comparable to the pre-determined EIS measurements.

13. The method of claim 12, wherein the proportions of the feedstock samples are adjusted so that the EIS measurements of the feedstock blend are within 5% of the pre-determined EIS measurements.

14. The method of claim 12, further comprising providing a look up table with EIS measurements of a plurality of reference refinery feedstock samples.

15. The method of claim 14, wherein the step of adjusting the proportions of the feedstock samples comprises using the look up table to adjust the proportions of the feedstock samples.

16. The method of claim 12, wherein the step of adjusting the proportions of the feedstock samples comprises using statistical techniques.

17. The method of claim 16, wherein the statistical techniques include at least one of Principal Component Analysis, Multivariate Least Squares Regression, Principal Component Regression, Pattern Recognition analysis, Cluster analysis, Neural Net analysis, and Group Methods of Data Handling.

18. The method of claim 12, further comprising analyzing the EIS measurements of each of the plurality of refinery feedstock samples using statistical techniques.

19. A method for optimizing blends of refinery feedstock, comprising:

providing a plurality of refinery feedstock samples with each feedstock sample being representative of a feedstock stream to the refinery;

performing impedance measurements at 10 kHz frequency as a function of temperature for each of the feedstock samples;

providing a database correlating impedance measurements with known corrosion performance of reference refinery feedstock;

using the impedance measurements of the refinery feedstock samples and the database correlating impedance measurements with corrosion performance of reference refinery feedstock to obtain a feedstock blend having desired impedance measurements correlating with an acceptable corrosion performance.