1、Evaluation of Treatment Technologies for Listed Petroleum Refinery Wastes HEALTH AND ENVIRONMENTAL SCIENCES DEPARTMENT API PUBLICATION NUMBER 4465 DECEMBER 1987 American Petroleum 11 Institute Evaluation of Treatment Technologies for Listed Petroleum Refinery Wastes Final Report Health and Environme
2、ntal Sciences Department API PUBLICATION NUMBER 4465 FIELD STUDIES CONDUCTED BY THE API WASTE TECHNOLOGY TASK FORCE REPORT PREPARED BY G. ROWE, CONSULTANT THE API WASTE TECHNOLOGY TASK FORCE WITH THE ASSISTANCE FROM DECEMBER 1987 American Petroleum Institute FOREWORD API PUBLICATIONS NECESSARILY ADD
3、RESS PROBLEMS OF A GENERAL NATURE. WITH RESPECT TO PARTICULAR CIRCUMSTANCES, LOCAL, STATE, AND FEDERAL LAWS AND REGULATIONS SHOULD BE REVIEWED. API IS NOT UNDERTAKING TO MEET THE DUTIES OF EMPLOYERS, MANUFAC- TURERS, OR SUPPLIERS TO WARN AND PROPERLY TRAIN AND EQUIP THEIR EMPLOYEES, AND OTHERS EXPOS
4、ED, CONCERNING HEALTH AND SAFETY RISKS AND PRECAUTIONS, NOR UNDERTAKING THEIR OBLIGATIONS UNDER LOCAL, STATE, OR FEDERAL LAWS. NOTHING CONTAINED IN ANY API PUBLICATION IS TO BE CONSTRUED AS GRANTING ANY RIGHT, BY IMPLICATION OR OTHERWISE, FOR THE MANU- FACTURE, SALE, OR USE OF ANY METHOD, APPARATUS,
5、 OR PRODUCT COV- ERED BY LETTERS PATENT. NEITHER SHOULD ANYTHING CONTAINED IN ITY FOR INFRINGEMENT OF LETERS PATENT. THE PUBLICATION BE CONSTRUED AS INSURING ANYONE AGAINST LIABIL- TABLE OF CONTENTS ChaDter Page Preface xiii 1 Executive Summary 2 Scope of Study Technologies Evaluated Data and Correl
6、ations Analytical Procedures 3 Mechanical Treatment 1 6 8 9 13 19 Overview 21 Belt Filter 22 Plate Filter 25 Rotary Drum Vacuum Filter 28 Equipment Description and Operation 22 Test Procedures Belt Filter Plate Filter Rotary Drum Vacuum Filter Test Results and Discussion Belt Filter Plate Filter Rot
7、ary Drum Vacuum Filter 30 30 32 34 35 38 58 72 4 Solvent Extraction 77 Overview 77 Equipment Description and Operation 79 Test Procedures 81 Test Results and Discussion 84 5 Thermal Treatment 92 Overview 92 Equipment Description and Operation 94 Test Procedures 95 Test Results and Discussion 96 6 Fi
8、xation 109 Overview 109 Process Description and Operation 110 Test Procedures, Results and Discussion 113 Chapter TABLE OF CONTENTS (CONT.) Page 7 Other Vendor Technologies (Pyrolysis) 129 Overview 129 Equipment Description and Operation 131 Test Procedures 132 Test Results and Discussion 132 8 Summ
9、ary and Perspective 136 Treatment Effectiveness Perspective 136 144 - iv - LIST OF FIGURES Figure Page 1-1 Reductions In Constituent Weights and TCLP Leachate Concentrations 5 2-1 Schematic of Waste Treatment Technologies Evaluated 7 2-2 Analytical Data and Correlations 10 3-1 Diagram of Belt Filter
10、 24 3-2 Plate Filter 26 3-3 Rotary Vacuum Filter 29 4-1 Simplified Steps of Solvent Extraction Process 78 5-1 General Thermal Treatment Process 93 6-1 Two-step Solidification Process 111 7-1 Pyrolysis Processor 130 8-1 Comparison of Alternate Treatment Technology Residuals to Incineration 149 8-2 Co
11、ncentrations In Raw Feeds and Residues 150 8-3 Integration of Waste Treatment Into a Refinery 151 8-4 Alternative Sequences, Treatment of Petroleum Wastes 152 -v- LIST OF TABLES Table 1-1 Average Concentrations of Total Residue 1-2 Average Concentrations of TCLP Leachate 2-1 Appendix VI11 Constituen
12、ts Analyzed 2-2 Constituents Analyzed as Indicator or Screening Compounds 3-1 Constituents of Refinery Wastes 3-2 Oil/Water/Solids Concentrations of Belt Filter Feed and Products - Refinery C2 3-3 Calculated Mass Balance Based on Oil/Water/Solids Analyses Belt Filter - Refinery C2 3-4 Constituent Co
13、ncentrations of Waste Feed and Belt Filter Cake, and Calculated 90 Reduction (Weight) - Refinery C2 3-5 TCLP Leachate Concentrations of Waste Feed and Belt Filter Cake - Refinery C2 3-6 Oil/Water/Solids Concentrations of Belt Filter, Feed and Products - Refinery C2 (Duplicate Run) 3-7 Calculated Mas
14、s Balance Based on Oil/Water/Solids Analyses Belt Filter - Refinery C2 (Duplicate Run) 3-8 Constituent Concentrations of Waste Feed and Belt Filter Cake, and Calculated % Reduction (Weight) - Refinery C2 (Duplicate Run) 3-9 Indicator TCLP Leachate Concentrations of Waste Feed and Belt Filter Cake -
15、Refinery C2 (Duplicate Run) 3-10 Oil/Water/Solids Concentrations of Belt Filter Feed and Products - Refinery C1 Page 2 4 14 15 20 39 40 41 42 43 44 45 46 49 - vii - LIST OF TABLES (CONT.) Table 3-11 Calculated Mass Balance Based on il/Water/Solids Analyses Belt Filter - Refinery C1 3-12 Constituent
16、Concentrations of Waste Feed and Belt Filer Cake, and Calculated % Reduction (Weight) - Refinery C1 3-13 TCLP Leachate Concentrations of Waste Feed and Belt Filter Cake - Refinery C1 3-14 Oil/Water/Solids Concentrations of Belt Filter Feed and Products Refinery C1 (Duplicate Run) 3-15 Calculated Mas
17、s Balance Based on Oil/Water/Solids Analyses Belt Filter - Refinery C1 (Duplicate Run) 3-16 Constituent Concentrations of Waste Feed and Belt Filter Cake, and Calculated % Reduction (Weight) - Refinery C1 (Duplicate Run) 3-17 TCLP Leachate Concentration of Waste Feed and Belt Filter Cake - Refinery
18、C1 (Duplicate Run) 3-18 Oil/Water/Solids Concentrations of Plate Filter Feed (Conditioned) and Products - Refinery B2 3-19 Calculated Mass Balance Based on Oil/Water/Solids Analyses Plate Filter - Refinery B2 3-20 Constituent Concentrations of Waste Feed and Plate Filter Cake, and Calculated % Reduc
19、tion (Weight) - Refinery B2 3-21 TCLP Leachate Concentrations of Waste Feed and Plate Filter Cake - Refinery B2 3-22 Oil/Water/Solids Concentrations of Plate Filter Feeds and Products - Refinery B1 Page 50 51 52 54 55 56 51 59 61 62 63 65 - viii - LIST OF TABLES (CONT.) Table Page 3-23 Calculated Ma
20、ss Balance Based on Oil/Water/Solids Analyses Plate Filter - Refinery B1 66 3-24 Constituent Concentrations of Waste Feed and Plate Filter Cake, and Calculated % Reduction (Weight) - Refinery B1 67 3-25 TCLP Leachate Concentrations of Waste Feed and Plate Filter Cake - Refinery B1 69 3-26 Oil/Water/
21、Solids Concentrations of Plate Filter Feeds and Cakes - Refinery B3 70 3-27 Indicator TCLP Leachate Concentrations of Waste Feed and Plate Filter Cake - Refinery B3 (First Test) 71 3-28,Indicator TCLP Leachate Concentrations of Waste Feed and Plate Filter Cake - Refinery B3 (Second Test) 73 Filter F
22、eeds and Cakes - Refinery V1 74 3-29 Oil/Water/Solids Concentrations of Vacuum 3-30 Indicator TCLP Leachate Concentrations of Waste Feed and Vacuum Filter Cake - Refinery V1 (First Test) 75 3-31 Indicator TCLP Leachate Concentrations of Waste Feed and Vacuum Filter Cake - Refinery V1 (Second Test) 7
23、6 4-1 Test Parameters for Pilot and Commercial Solvent Extraction Units 82 4-2 Oil/Water/Solids Concentrations of Solvent Extraction Feed and Products 86 4-3 Calculated Mass Balance Based on Oil/Water/Solids Analyses Solvent Extraction 88 4-4 Constituent Concentrations in Feed and Product Solids and
24、 Calculated % Reduction (Weight) - Solvent Extraction 89 - ix - Table 4-5 5-1 5-2 5-3 5-4 5-5 5-6 5-7 5-8 5-9 6-1 LIST OF TABLES (CONT.) Page TCLP Leachate Concentrations of Waste Feed and Product Solids - Solvent Extraction 91 Oil/Water/Solids Concentrations of Product Solids from Thermal Treatment
25、 Tests 97 Constituent Concentrations in Feed and Product Solids Low Temperature Thermal Treatment of Belt Filter Cake Feed - Refinery C1 101 Constituent Concentrations in Feed and Product Solids High Temperature Thermal Treatment of Belt Filter Cake Feed - Refinery C1 102 Constituent Concentrations
26、of Waste Feed and Product Solids Low Temperature Thermal Treatment of Plate Filter Cake Feed - Refinery B1 103 Constituent Concentrations in Feed and Product Solids High Temperature Thermal Treatment of Plate Filter Cake Feed - Refinery B1 104 TCLP Leachate Concentrations of Waste Feed and Low Tempe
27、rature (350F) Thermally Treated Belt Cake - Refinery C1 105 TCLP Leachate Concentrations of Waste Feed and High Temperature (550F) Thermally Treated Belt Cake - Refinery C1 106 TCLP Leachate Concentrations of Waste Feed and Low Temperature (350F) Thermally Treated Plate Cake - Refinery B1 107 TCLP L
28、eachate Concentrations of Waste Feed and High Temperature (550OF) Thermally Treated Plate Cake - Refinery B1 108 TCLP Leachate Concentrations of API Separator Sludge and Residue from Fixation Process #l - Refinery A 116 -x- LIST OF TABLES (CONT.) Table Page 6-2 6-3 6-4 6-5 6-6 6-7 6-8 6-9 6-10 7-1 7
29、-2 8-1 TCLP Leachate Concentratiosn of Slop Oil Emulsion Solids and Residue from Fixation Process #i - Refinery A TCLP Leachate Concentrations of Plate Filter Cake and Residue from Fixation Process #i - Refinery B1 117 118 TCLP Leachate Concentrations of Belt Filter Cake and Residue from Process #i
30、- Refinery C1 119 indicator TCLP Leachate Concentrations of Plate Filter Cake and Residue from Process #2 - Refinery B1 121 Indicator TCLP Leachate Concentrations of Belt Filter Cake and Residue from Process #2 - Refinery C1 Indicator TCLP Leachate Concentrations of Thermally Treated Plate Filter Ca
31、ke and Residue from Fixation Process #2 - Refinery B1 122 123 Indicator TCLP Leachate Concentrations of Thermally Treated Belt Filter Cake and Residue from Fixation Process #2 - Refinery C1 124 Indicator TCLP Leachate Concentrations of Belt Filter Cake and Residue from Fixation Process #3 - Refinery
32、 C1 127 Indicator TCLP Leachate Concentrations of Plate Filter Cake and Residue from Fixation Process #3 - Refinery B1 Total Constituent Concentrations of Waste Feed and Solid Residue from the Pyrolysis Process - Refinery E Indicator TCLP Leachate Concentrations of Solid Residue from the Pyrolysis P
33、rocess - Refinery E Constituent and TCLP Concentratiosn - Waste Feed and Product Solids - Mechanical Treatment 128 133 135 137 - xi - LIST OF TABLES (CONT.) Table Page 8-2 Constituent and TCLP Concentrations - Waste Feed and Product Solids - Solvent Extraction 139 8-3 Constituent and TCLP Concentrat
34、ions - Mechanical Plus Thermal Treatment 140 8-4 TCLP Concentrations - Raw Wastes and Fixed Products - Fixation 142 8-5 TCLP Concentrations Filter Cakes and Fixed Products - Fixation 143 8-6 TCLP Concentrations Thermally Treated Cakes and Fixed Product - Fixation 145 8-7 Constituent and TCLP Leachat
35、e Concentrations - Waste Feed and Product Solids - Pyrolysis 146 - xii - PREFACE Provisions for the land disposal ban of the 1984 RCRA Amend- ments, require EPA to develop best-demonstrated available tech- nology (BDAT) treatment standards for selected hazardous wastes including listed refinery wast
36、es. The treatment standards in the proposed ruling of April 8, 1988 are based on incineration treatment efficiencies derived from test burns of listed refinery wastes. Land treatment units must comply with the proposed rule unless they fulfill the requirements of a “no migration petition“. Refinerie
37、s without permitted land treatment units will be forced to arrange for incineration of their wastes prior to land disposal unless other technologies become commercially available which can meet the proposed BDAT standards. Due to limited incinerator capacity in the United States, the cost and diffic
38、ulties in permitting incinerators, and recent emphasis on source reduction and recycling, alternatives to incineration which recycle the toxic constituents of the wastes are of interest to the petroleum industry. The petroleum refining industry utilizes many different treatment/disposal schemes to m
39、anage listed hazardous wastes. The decision as to which scheme to use at a particular site, on a particular waste is a function of many factors, such as waste characteristics, available land, local environmental regulations, permitting, and public opinion. Clearly, there is no one treatment scheme w
40、hich is applicable for all petroleum refining wastes, at all locations. Currently, the most widely used treatment technology within the industry for oily wastes is land treatment. However, Congress has included land treatment as a form of disposal under the land disposal bans. This study was underta
41、ken in order to determine how effective other treatment technologies could be. - xiii - API has previously submitted comments (September 1986) to the EPA regarding technical problems associated with the Toxicity Characteristic Leaching Procedure (TCLP) and its application to oily wastes. The submiss
42、ion of TCLP data in this report should not be construed as a deviation from APIs original position regarding TCLP. These data are submitted in an attempt to demonstrate the treatment efficiency of several technologies by applying the same TCLP criteria which were used by EPA in developing the solven
43、ts/dioxin rule (Federal Register November 6, 1986). To provide a more comprehensive waste treatment study, technology vendors who were not API contractors were invited to submit data to the API for review and evaluation. In order to qualify for inclusion in the final report, these vendors had to tre
44、at listed refinery wastes, adhere to the API sampling and analytical protocols, and submit operating and test data by February 15, 1987. The only noncontracted vendor who met these criteria was one offering a pyrolysis treatment process. These data are included in this report. API gratefully acknowl
45、edges the efforts of the Rocky Mountain Analytical Laboratory, which supplied all of the analytical data; the participating refineries, which provided listed wastes and treatment process data; the participating equipment vendors; Risk Science International, for writing the interim report; and member
46、s of the API Waste Technology Task Force, who planned the project and brought it to fruition. Special recognition is given to Hugh Dickey (Chevron) for the study design, Frank Prince, Ph.D., the API project manager, Piyush Shah, Ph.D. (Exxon) for structuring the analytical data tables, Richard Stalz
47、er (Sohio) and Bill Deever, Ph.D. (Texaco) for the mechanical drawings, and ReNaye Williams of API for typing the manuscript. - xiv - CHAPTER 1. EXECUTIVE SUMMARY A number of technologies for the treatment of listed petroleum refinery oily wastes were evaluated in this study. The tech- nologies stud
48、ied were mechanical treatment (filtration), solvent extraction, thermal treatment (drying), chemical fixation and pyrolysis. In several cases the application of two treatment technologies in series was studied, e.g. filtration followed by drying, drying followed by fixation. No attempts were made to
49、 develop limits of operability for the subject treatment technologies nor was consideration given to the cost of various technologies. As evaluation tools, the reductions in mass from feed to product residues and the reductions in constituent leachate concentrations from feed to product residues were evaluated. All of the technologies tested produced a residue of substantially reduced hazard, as measured by leachable concentrations (using TCLP) of hazardous constituents in the product solids. Four of the technologies also reduced the total constituent concentrations. Table 1-1 allows a
