Hyrdazine Replacement

Working Across the Border

Piping System Design Requirements

Dec 2005

Institute of Power Engineers

Editor- George Reid Contributors Tony Conner TBP Industrial Steam Systems A. Banweg, D. G. Wiltsey and B. N. Nimry, Nalco Company Rheal Caron, Director of Fuel Gas Generation, Suez Energy Generation NA, Inc. R. A. Clarke, President and Chief Operating Officer PanGlobal Training Systems Ltd.

3 From The Editor 4 Carbohydrazide — A Hydrazine Replacement: 10 Years of Utility Experience 8 Canadian Perspective Working in the United States 9 Design Requirements Pertaining to Specific Piping Systems 11 Power Engineering A North American Profession in Transition

Institute of Power Engineers

Ta b l e o f C o n t e n ts

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From The Editor Tomorrow Never Knows

Over the past number of months one of the top stories in the news has been the ever

increasing price of oil. Weather you subscribe to the idea of peak oil, the power of supply and demand, or any of other theory the arguable reality is the price of crude has increased. This price increase has had multiple impacts, especially in the power generation industry. Just look to Calpine for the proof. The inevitable question is are we to continued our crude driven lust for power or will we look for alternatives.

Our neighbours to the south are gearing up coal plants as a hedge against higher energy costs with new nuclear plants being openly discussed. Here in Canada we have a political will to adhere to the Kyoto protocol but are now just starting to see some of it’s full costs. What direction do we take? The issue is more complex, as some provinces like Ontario deregulate their hydro markets yet with governmental influences. This last twist has power generators even more cautious to invest in new capacity with both the public and industry left with a dwindling supply. In is the climate we should be looking for power alternatives.

In a previous IPE magazine issue we looked at the Dynamotive- Erie Flooring project of converting biomass into bio-oil for a cogeneration plant. This is the start of an innovative paradigm shift. Over the last four decades energy alternatives have been researched some being solar cells, wind turbines, fusion reactor etc….

In the next couple of issues we’ll look at some of the more exotic power generation

alternatives. Two years ago if you told someone crude oil would be at today’s prices they wouldn’t have believed you. The same could be said for our future energy sources as the Beatles sang Tomorrow Never Knows.

George Reid The Editor

ABSTRACT Carbohydrazide, in just ten years time, has replaced hydrazine in 20% of the United States electric utility industry. By far the most widely used replacement for hydrazine, carbohydrazide is now in use in over 275 utility boilers, accounting for over 60,000 MW of installed capacity. It is timely to report on this experience, which covers the entire range of utility boiler pressures, including 3500 psi supercritical units. Data will be presented on the effects of carbohydrazide use on: lay-up, start-up, chemical cleaning frequency, and cycle corrosion control.

INTRODUCTION

Carbohydrazide was originally introduced to the utility industry as a “safer-to-use” alternative to hydrazine. It was then, and still is — in its commercialized form — a safer-to-handle product, not requiring elaborate, closed handling and feeding systems. Neither is the commercialized product subject to the several pieces of recent legislation dealing with hazardous materials and disposal of packaging materials. Carbohydrazide has gained its market position, not on the safety-related issues, but rather because of itsrepeatedly demonstrated performance benefits. Moreover, these benefits have been achieved without producing any disruption to normal condensate/ feedwater/boiler water/steam parameters designated by the EPRI Consensus Guidelines. These benefits can be listed as: • Improved low temperature reactivity with oxygen • Greatly reduced corrosion in all pre-boiler condensate/ feedwater system components, as evidenced by consistent reductions in transported corrosion products of 50 to 85% • Reductions in chemical cleaning requirements —especially notable for cycling units • Significant improvement in desuperheating water quality, minimizing this source of turbine foulants • Reduced start-up times following short or longterm outages (especially following lay-up with carbohydrazide) • Superior lay-up program characteristics This paper will present case histories that demonstrate several of these benefits. In addition, more recently developed, and corroborating, laboratory data will be shown.

Carbohydrazide — A Hydrazine Replacement: 10 Years of Utility Experience By A. Banweg, D. G. Wiltsey and B. N. Nimry, Nalco Company

CHEMISTRY OF CARBOHYDRAZIDE REACTION WITH OXYGEN For over fifty years, hydrazine has been the utility industry oxygen scavenger of choice, primarily because it contributes no dissolved solids to the boiler system. Its direct reaction with dissolved oxygen is classically shown as: N2H4 + O2 → 2H2O + N2 At the 1957 American Power Conference, Dickenson, Felgar, and Pirsh reported that the above reaction proceeds very slowly at the low temperatures common to the low temperature end of a utility cycle (Figure 1).1 As a consequence, the low temperature end of the cycle is rarely, if ever, completely protected when hydrazine is used. In the early 1980’s, carbohydrazide* was introduced to the utility industry as a replacement for hydrazine. Carbohydrazide, a derivative of hydrazine, reacts with dissolved oxygen along two pathways: Direct reaction (<275�F/135�C): (N2H3)2CO + 2O2 → 2N2 + 3H2O + CO2 Indirect reaction (beginning at >275�F/135�C): (N2H3)2CO + H2O → 2N2 H4 + CO2 (3) 2N2H4 + 2O2 → 4H2O + 2N2 (4)

It should be noted from Equation 2 that oxygen scavenging is accomplished at low temperatures by the carbohydrazide molecule itself; no conversion to hydrazine is required. At higher temperatures, the reaction with dissolved oxygen is with either carbohydrazide or hydrazine — or both — depending upon system residence time, fluid temperature, and,to some extent, system metallurgy (Figure 2).

METAL PASSIVATION Laboratory work, and subsequent field experience, have shown carbohydrazide to be an extremely effective metal passivator. Passivation reactions of carbohydrazide can be shown as: 12Fe2O3 +(N2H3)2CO → + 8Fe3O4 + 3H2O + 2N2 + CO2 (5) 8CuO +(N2H3)2CO → + 4Cu2O + 3H2O + 2N2 + CO2 (6) Figure 1 — Effect of temperature on N2H4 –O2 reaction efficiency*. Time of 0.83 minutes in carbon steel tubing.

Figure 2 — Typical carbohydrazide-to-hydrazine conversion pattern Early laboratory data comparing the passivation capability of various oxygen scavengers was based upon the solubility of the oxide film in an 18% HCl solution.2 In recent years, ex-situ linear polarization measurements were performed on laboratory-generated specimens to determine the degree of passivation attained by various materials.3 To support this work, a process simulation unit (FEEDSIM) that mimics a condensate/ feedwater heater array was constructed to enhance the understanding of preboiler passivation (Figure 3). The FEEDSIM unit can simulate specific chemistries, specific metallurgies, specific heat fluxes, etc. Table 1 summarizes one set of test conditions. Specimens are removed from FEEDSIM, dried, and then properly stored in nitrogen- blanketed containers for subsequent electrochemical and scanning electron microscope (SEM) analyses.

The use of this new laboratory procedure has confirmed the earlier data that showed carbohydrazide to be a better low temperature passivator than hydrazine. Results of ex-situ linear polarization tests on untreated, hydrazine-treated, and carbohydrazidetreated FEEDSIM tube specimens are summarized in Figure 4. The bigger the Rp (polarization resistance) value, the more protective the oxide film that has been formed on the metal surface. It is evident from this graph that carbohydrazide, under these test conditions, is a much more effective metal passivator than hydrazine at temperatures below 350�F (180�C). Table 2 summarizes the physical observations made on the specimens. Both the untreated and the hydrazine- treated specimens exhibited pitted surfaces at temperatures below 280�F (138�C) and 205�F (96�C), respectively. Confirmation of the laboratory data in an actual field application of carbohydrazide has been published previously,4 but bears repeating at this point. The data derived from a carbohydrazide application in an 800 MW supercritical unit is typical of that noted on essentially all units that have converted from hydrazine to carbohydrazide. Figure 5 shows that the “passivation demand” for carbohydrazide — even after years of treating this unit with hydrazine — took almost two months to satisfy. The final dosage required to produce the control residual in the feedwater was less than 50% of that needed originally.

Where are you from? Canada you say, eh! In my experience, Americans seem to know little about Canadians especially in the South. Working and living in the US over the last seven years in the Power Industry has opened my eyes to how Canadians are received. When Canadians are doing business with US counterparts, we are well respected in regards to our knowledge of Power Plants. I am not sure exactly what it is Americans admire about us but I believe the education we receive to be a part of it. My experience of our Power Plant training compared to the US systems may be a part of why Canadians are so well respected. In Canada, we have a uniform system for Power Engineers that is inter-provincial. In the US, there are several different types of education for Power Engineers. At SUEZ Energy NA, the reasons that Canadians are so well accepted may be due to the cultural diversity within the organization that emphasizes training, experience, shared values and accomplishments. In many situations I feel as though I am treated as a Professional Engineer. I go out of my way to let people I work with and let business counterparts know that I am not a Professional Engineer; however it doesn’t seem to make a difference to them. I have never had an experience or a feeling of discrimination as a Canadian. I find that Americans tend to accept us quickly and warmly. I say this because I have several people who I work with who are also from Canada. We have been very well accepted without prejudice. There is a feeling that one can go far in the US if one is willing to apply one self. I felt this way in Canada also, however there are more opportunities in the US than there are in Canada. As a Canadian living in the US, there is a lot of subtle pressure to become an American. It is difficult to keep a Canadian identity in a country that has so much pride of being American. One of the attributes I believe Americans like about Canadians working in the US is the work ethic that Canadians have. Americans value hard work and people who work hard are treated well and are well compensated. Unfortunately, I find it much more difficult to balance family life with work in the US then I did working in Canada. Canadians value their time off while Americans are perceived as valuing more time worked. However this is only my experience, many US companies require employees to work longer hours due to competitive demands. I have enjoyed working in the US since 1998; however I will always miss certain things about my homeland, Canada. Rheal has been in the power generating field for 26 years beginning by working as an operator in a power plant and graduating with a First Class Operating Engineers License. In 1988 Rheal became Chief Engineer of Labatt’s Breweries in London Ontario Canada and was promoted to Plant Services Manager in 1990. As Plant Services Manager, Rheal was responsible for 100 skilled craftsman, 11 supervisors and responsible for maintenance of all Brewery equipment and Packaging equipment. At Labatt’s, Rheal installed the first combustion turbine cogeneration system in a Brewery in Canada in 1992. In 1994, Rheal joined Tractebel as Plant Manager of West Windsor Power. In 1998 Rheal was promoted to Director of Operations responsible for several combined cycle plants. Today Rheal is the Director of Fuel Gas Generation for SUEZ Energy Generation NA. Rheal is presently enrolled in Bachelor Science Commerce program at the University of Phoenix.

Canadian Perspective Working in the United States Written by: Rheal Caron, Director of Fuel Gas Generation, Suez Energy Generation NA, Inc.

The ASME B31 series of pressure piping codes lay out the minimum requirements for this category of piping. The ASME B31.1 Power Piping Code covers boiler and compressor plant piping, along with distribution piping in general industrial plants, such as steam, condensate, compressed air, etc. Within B31.1 is a specific section on “Boiler External Piping”. Part 6

SYSTEMS 122 DESIGN REQUIREMENTS PERTAINING TO SPECIFIC PIPING SYSTEMS 122.1 Boiler External Piping; in Accordance With Para. 100.1.2(A) – Steam, Feedwater, Blowoff and Drain Piping This section has beefed-up standards that address the more severe service conditions found near boilers. Examples include feedwater piping that sees the highest pressure in any steam plant, blowoff piping goes from atmospheric pressure & ambient temperature to operating boiler conditions instantly, then just as quickly off again, several times per day. Following are some excerpts regarding blowoff piping taken from B31.1. (“Blowdown” refers to continuous blowdown or CBD, and “blowoff” refers to what is often called bottom (intermittent) blowdown.) Note that when code documents refer to the value of “P” they mean the boiler or piping safety valve setting, NOT the operating pressure. 122.1.4 Blowoff and Blowdown Piping. (A.1) The value of P to be used in the formulas in para. 104 shall exceed the maximum allowable working pressure of the boiler by either 25% or 225 psi (1550 kPa) whichever is less, but shall not be less than 100 psig [700 kPa (gage)]. (A.3) All pipe shall be steel. Galvanized steel pipe and fittings shall not be used for blowoff piping. When the value of P does not exceed 100 psig, the fittings shall be bronze, cast iron, malleable iron, ductile iron, or steel. When the value of P exceeds 100 psig, the fittings shall be steel and the thickness of pipe and fittings shall not be less than that of Schedule 80 pipe. 122.1.7. (C.4) For all boilers [except electric steam boilers having a normal water water content not exceeding 100 gal (380 l), traction-purpose, and portable steam boilers; [see (C.11) and (C.12) below] with allowable working pressure in excess of 100 psig [700 kPa (gage)], each bottom blow off pipe shall have two slow-opening valves, or one quick-opening valve or cock, at the boiler nozzle followed by a slow-opening valve. All valves shall comply with the requirements of (C.5) and (C.6) below.

DESIGN REQUIREMENTS PERTAINING TO SPECIFIC PIPING SYSTEMS by Tony Conner of TBP industrial Steam Systems

Note: A “slow opening valve” is defined in ASME B31.1 as requiring at least five 3600 turns to go from full closed to full open. (C.5) When the value of P required by para. 122.1.4 (A.1) does not exceed 250 psig [1750 kPa (gage)], the valves or cocks shall be bronze, cast iron, ductile iron, or steel. The valves or cocks, if of cast iron, shall not exceed NPS 2-1/2 and shall meet the requirements of the applicable ASME Standard for Class 250, as given in Table 126.1, and if of bronze, steel, or ductile iron construction, shall meet the requirements of the applicable standards as given in Table 126.1 or para. 124.6 (C.6) When the value of P required by para. 122.1.4(A.1) is higher than 250 psig [1750 kPa (gage)], the valves or cocks shall be of steel construction equal at least to the requirements of Class 300 of the applicable ASME Standard listed in Table 126.1.The minimum pressure rating shall be equal to the value of P required by para. 122.1.4(A.1). The above is a brief overview of just some of the requirements outlined in the BEP section of ASME B31.1. The Alberta Boiler Safety Association has an Information Bulletin ALERT regarding a fatality in that province that is a direct result of people failing to realize the code requirements for a particular application. This fatal accident specifically involved a boiler blowoff valve failure. In addition, the ABSA has a short article addressing “Boiler External Piping” in their Sept 05 newsletter.

http://www.tbpindustrial.com/

US and Canadian Comparisons - Accidents From 1991-2000 there were 28,025 boiler and pressure vessel accidents reported to the Na-tional Board. These accidents resulted in 662 serious injuries and 121 fatalities. Of these accidents, 79% were attributed to operator error. These numbers do not include incidents in States where there are no boiler laws or where the inspections are not carried out by the jurisdictions.

In addition to the cost of human lives and injuries, these statistics are even more significant when one considers the costs of: replacing damaged equipment, loss of production, rehabilitating in-jured workers, and increased insurance premiums. By comparison, in Canada there were approxi-mately 500 operator accidents during the same (1991-2000) period. The Canadian accidents resulted in 2 deaths and less than 20 injuries. The National Board statistics include all the incidents reported by the Canadian jurisdictions, but do not include incidents in the States where there are no boiler laws or where the inspections are not carried out by the jurisdictions.

In 2003, the numerical comparison shows similar results. Total incidents reported to the Na-tional board sum to 1489. Of this sum, only 25 come from Canada’s jurisdictions.

The size differences between Canadian and American economies and population are often used as a basis to compare results. In the case of boiler operations, a closer comparison can be made based on specific industry information. Power Engineering professionals work within approximately a dozen major industries, or Market Segments, irrespective of geographical considerations. They are employed in schools, hospitals, hotels, apartment buildings, shopping malls, airports, power plants, industrial and manufacturing plants, breweries, co-generation plants, petro-chemical plants, office and commercial buildings, government facilities and other workplaces. Approximate workplace (employer) quantities for these segments can be seen in Table 1.

Table 1 further subdivides employer count by the nature of the workplace, specifically into Indus-trial and Facility boiler applications. This distinction can best be understood as a separation between low-pressure and higher-pressure power plants. Typically, except in the case of very large buildings / com-plexes, Facility applications will utilize the predominantly lower operating pressures of heating boilers.

Power Engineering A North American Profession in Transition- Part 2

R. A. Clarke,

President and Chief Operating Officer

PanGlobal Training Systems Ltd.

Table 1: Workplace Quantity by Market Segment Companies in Segment: Qty CAN Qty US

Note: *Quantities are rounded off to nearest hundred.

TABLE 2: INDUSTRY SEGMENT TO POWER ENGINEER EMPLOYMENT Segment: Ratio: CNcom: CNemp: UScom: USemp:

Utility companies 300 6,400 Waste to Energy companies 100 1,100 Food & Beverage Processing plants 4,800 35,500 Industrial Manufacturing plants (3) 15,300 148,300 Mining, Refining & Smelting (4) 800 3,200

Petroleum plants & pipelines (5) 400 9,900 Pulp, Paper and Forest Products 800 3,000

Subtotal, “Industrial” = 22,500 207,400 Commercial buildings (1) 17,200 211,600 Hospitals, Prisons (2) 2,000 38,300 Schools & Educational facilities 18,300 165.000

Subtotal, “Facility” = 37,500 414,900 Total companies = 60,000 622,300

Utilities 1:16 (1) 300 4,800 6,400 102,400 Waste to Energy 1:12 (2) 100 1,200 1,100 13,200 Food & Beverage 1:4 (3) 4,800 19,200 35,500 142,000 Manufacturing 1:2 (3) 15,300 30,600 148,300 296,600 Mining, & Smelting 1:12 (4) 800 9,600 3,200 38,400

Petroleum & pipelines 1:12 (4) 400 4,000 9,900 99,000 Pulp & Paper 1:12 (4) 800 9,600 3,000 36,000 Subtotal, Industrial 22,500 79,000 207,400 727,600 Commercial buildings 1:1 (5) 17,200 17,200 211,600 211,600 Hospitals, Prisons 1:4 (3) 2,000 8,000 38,300 153,200 Schools, Educational 1:1 (5) 18,300 18,300 165.000 165,000

Subtotal, “Facility” 37,500 43,500 414,900 529,800 Totals= 60,000 122,500 622,300 1,257,400

A number of assumptions were made on the numbers of staff required to operate the facilities which are indicated in the notes. The overall direct Ratio of Companies which have boilers in Canada vs the United States is 60,000:622,300. When translated to staff operating the boilers in these companies the ratio be-comes 122,500:1,257,400. In both cases a ratio of approximately 1:10 will be assumed and used. The Canada:US ratio, then, should be 1:10, based on both employee population and industrial base. Even without taking into consideration that some of the incidents in the States might not have been included, the actual rate is closer to 1:60.

What has created this significant gap in the safety of the industry between the two countries?

US and Canadian Comparisons – Design and Construction The American Society of Mechanical Engineers (ASME), Boiler and Pressure Vessel Code is a uniform set of technical requirements for the design, construction and installation of Boiler and Pres-sure Vessels. These codes have been placed into law by a majority of the jurisdictions in the USA and in all Canadian Provincial legislation. These standards are administered throughout North America by the National Board of Boiler and Pressure Vessel Inspectors (NBBI) who have developed uniform inspection rules. Independent third party or government inspectors are certified to perform the appropriate inspections. The existence of a common set of design and manufacturing standards through the use of ASME Codes and the enforcement of code adherence through NBBI inspections effectively removes manu-facturing differences as a causative factor in the disparity in accident rates

US and Canadian Comparisons - Operator Certification and Training If Design and Construction of boilers are governed by the same set of controls in the two coun-tries, the operation and maintenance of the boilers must be looked at as the main source of disparity in safety records. The critical variables here are the experience, training and certification of operations staff. In the United States, Power Engineering Skills development is provided in a number of ways including; Colleges and Private Trainers, On-The-Job mentoring, and Manufacturer’s training. These efforts use non-uniform sets of training materials, which are generally lacking in instructional design and which have been developed either from the educator's individual background or from reference materials not designed for instruction.

The largest independent certifying group in the United States is the National Institute for the Uniform Licensing of Power Engineers, Inc. (NIULPE). NIULPE is a nationally registered, third-party licensing agency working to establish national standards of competence for boiler firemen and water-tenders, engineers, operators, examiners, instructors, and the licensing agencies currently in ex-istence.

In Canada the situation is very different. A national standard of competence for Certification of Power Engineers does exist countrywide under the auspices of the Association of Chief Inspectors, who maintain a common training Syllabi. Examinations are administered by SOPEEC, a sub-committee of ACI, and are delivered from a common assessment bank maintained by SOPEEC’s Co-ordinator.

Educators in Canada have been delivering formal power engineering education and training since the 1920’s. The training is currently being delivered by more than 50 community colleges and technical institutes in all 10 provinces and 3 territories. There exists also a large network of high quality, corpo-rate and private trainers.

Key to this system is the use of a single and consistent set of training syllabi. Training materi-als developed to support the syllabi are submitted for endorsement. The materials are then certified by both SOPEEC and ACI as providing the appropriate level and type of content to meet the level and objectives of the training syllabi across Canada. SOPEEC, through its subcommittee, the Interprovin-cial Power Engineering Curriculum Committee (IPECC) monitors the courseware yearly and requires a mandatory five year product renewal.

The only set of materials to date to have successfully met these rigorous requirements is devel-oped and maintained by PanGlobal Training Systems Ltd., a non-profit corporation owned by three post secondary technical institutes in Canada, SAIT, NAIT and BCIT

Creating a Standard for Certification and Training The creation of a complete and effective certification and training standard is a major task re-quiring a large staff with multiple, specialized skills. Central to this concept is the syllabus, which specifies what will be taught in a program and how students will be evaluated. Syllabi can only be created through the participation of all stakeholders. For developers, the syllabus provides the frame-work around which the content is developed. Developers must meet the specifications of the syllabus in order for their course to be accepted by the profession.

In Canada’s system, National Board members control the certification and training syllabi throughout the country, and review them regularly (at least every five years) to ensure they still meet the profession’s needs and jurisdictional regulatory requirements. They are advised in this by stake-holder groups including: Examiners, Educators, and Industry representatives.

Developers of training materials use the Canadian syllabi as a guide for the creation of course-ware. This courseware can then be provided back to the various stakeholders in the system for en-dorsement of its value. Just as the syllabi require review, so too does the approved courseware, usually on a similar schedule.

Creation of Certification Standards requires input from Legislators, Regulators, Industry, Ex-aminers, Educators, Insurers, and Individuals.

Content development requires Authors, Instructional Designers, Artists, Editors, Data Entry Staff and Project Managers. Training delivery requires many Trainers, Administrators and Support Staff. Usually, it is not feasible for any single stakeholder group to undertake the full scale develop-ment of either a certification or training program. Instead, creating an effective solution relies on co-operation.

Reducing the Safety Gap- A Single North American Certification System

NIULPE has recently adopted the ACI training syllabi as the basis of their certification sys-tem. NIULPE and SOPEEC are currently investigating the synergies possible within a common vi-sion of a single North American certifying standard. The current standard shared by NIULPE and SOPEEC generally meets the needs of all Power Engineers given that all boilers are created under the same set of codes. There are differences be-tween the two systems given the differing nature of the jurisdictional requirements in Canada and the United States. Although rigorously maintained a Syllabi designed to meet the needs of Canada’s Ju-risdictions only cannot be as efficient when applied to any US situation and so the current model can-not be used to directly compare the effect of rigorous certification and training on improvement of safety. The Canadian Certification Standard is controlled by Canada’s National Board Members. It’s Jurisdictions singly align themselves with the national standard and examine from a common data-base. They accept extra-provincially credentialed individuals from other provinces and territories. To achieve a North American Standard, similar control needs to be held by a group with a similar man-date. This Standard could then be adopted by individual jurisdictions which would then recognize the standard training and certification received both from within its borders and by qualified individu-als from outside.

Conclusions and Recommendations

In the 100 year history of regulation in North America many improvements have occurred in the monitoring of boiler design and construction practices. A single standard has evolved, developed by the ASME, adopted by almost all jurisdictions, and administered by the National Board.

An operator certification and training standard has also evolved and has been standardized for Canadian Jurisdictions. Because of the uniform standard for the design and construction of boilers, the differences in accident rates between US and Canadian jurisdictions must be linked to the lack of a uniform and consistent standard of Operator Certification and Training across the United States.

The majority of these accidents are a result of human error and many of them can be pre-vented through a proper training program. By looking at individual corporate experiences it is clear that safety improves when appropriate operator training is implemented.

The ultimate solution to this problem must involve all stakeholders. Critical success of any ultimate solution is it’s control by the uniform vision of a group of internationally credentialed indi-viduals, at the top of this profession, who together have the mandate to develop and maintain a North American Standard.

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