CN111287817A - Organic Rankine cycle power generation system for recycling black water flash steam waste heat - Google Patents

Organic Rankine cycle power generation system for recycling black water flash steam waste heat Download PDF

Info

Publication number
CN111287817A
CN111287817A CN202010260879.9A CN202010260879A CN111287817A CN 111287817 A CN111287817 A CN 111287817A CN 202010260879 A CN202010260879 A CN 202010260879A CN 111287817 A CN111287817 A CN 111287817A
Authority
CN
China
Prior art keywords
pipe
rankine cycle
power generation
waste heat
evaporator
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202010260879.9A
Other languages
Chinese (zh)
Inventor
李健
袁智威
雷卫伟
黄建
宿立强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing Tianheating Technology Co Ltd
Nanjing Chengzhi Clean Energy Co Ltd
Original Assignee
Nanjing Tianheating Technology Co Ltd
Nanjing Chengzhi Clean Energy Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing Tianheating Technology Co Ltd, Nanjing Chengzhi Clean Energy Co Ltd filed Critical Nanjing Tianheating Technology Co Ltd
Priority to CN202010260879.9A priority Critical patent/CN111287817A/en
Publication of CN111287817A publication Critical patent/CN111287817A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01KSTEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K27/00Plants for converting heat or fluid energy into mechanical energy, not otherwise provided for
    • F01K27/02Plants modified to use their waste heat, other than that of exhaust, e.g. engine-friction heat
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01DNON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D15/00Adaptations of machines or engines for special use; Combinations of engines with devices driven thereby
    • F01D15/10Adaptations for driving, or combinations with, electric generators
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01KSTEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K25/00Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for
    • F01K25/08Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using special vapours
    • F01K25/10Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using special vapours the vapours being cold, e.g. ammonia, carbon dioxide, ether

Abstract

The invention relates to an organic Rankine cycle power generation system for recovering waste heat of black water flash steam, which comprises a Rankine cycle system consisting of an expander, a condenser and an evaporator, wherein an exhaust port of the expander sequentially passes through a first pipe of the condenser and a second pipe of the evaporator and then is connected with an air inlet of the expander; a second pipe of the condenser is connected with the cooling tower in series to form a closed-loop condensation circulating system; the first pipe of the evaporator and the second pipe of the front heat exchanger are connected in series to form a closed-loop hot water system; the inlet and the outlet of the first pipe of the front heat exchanger are respectively connected with a high-pressure flash tank and a low-pressure flash tank; the high-pressure flash tank is also connected with the low-pressure flash tank after passing through a cooler; the expander is connected with a generator. The invention has reasonable design and convenient control, can fully recover the waste heat of the black water flash steam, is applied to the power generation of a Rankine cycle system, effectively improves the utilization rate of energy and realizes the sustainable development of ecological environment.

Description

Organic Rankine cycle power generation system for recycling black water flash steam waste heat
Technical Field
The invention relates to a heat energy system, in particular to an organic Rankine cycle power generation system, and specifically relates to an organic Rankine cycle power generation system for recovering waste heat of black water flash steam.
Background
Energy conservation and emission reduction are basic national policies of energy development in China, and the core contents of energy conservation and emission reduction are to reduce energy waste and pollutant emission. In the coal chemical production process, a large amount of high-temperature slag-containing black water is generated, and the black water enters a high-pressure flash tank to generate flash steam of the black water. The recycling of the waste heat of the black water flash steam is an important content of energy conservation and emission reduction in coal chemical enterprises.
At present, the common method is that the black water flash steam is cooled into condensate through a cooler, and the condensate enters a low-pressure flash tank for recycling. In the way, the waste heat of the black water flash steam is in a waste state, so that not only is no economic benefit generated, but also a large amount of circulating cooling water is consumed. Therefore, there is a need for improvements to existing processes to improve the overall energy utilization of the system.
Disclosure of Invention
The invention aims to solve the problems in the use of black water flash steam at present, and provides an organic Rankine cycle power generation system for recovering the waste heat of the black water flash steam, which can fully recover the waste heat of the black water flash steam and apply the waste heat to power generation, effectively improve the utilization rate of energy and realize energy conservation and environmental protection.
The technical scheme of the invention is as follows:
an organic Rankine cycle power generation system for recovering waste heat of black water flash steam comprises an organic Rankine cycle power generation system consisting of an expander, a generator, a condenser and an evaporator, wherein an exhaust port of the expander sequentially passes through a first pipe of the condenser and a second pipe of the evaporator and then is connected with an air inlet of the expander; a second pipe of the condenser is connected with the cooling tower in series to form a closed-loop condensation circulating system; the first pipe of the evaporator and the second pipe of the front heat exchanger are connected in series to form a closed-loop hot water system; the inlet and the outlet of the first pipe of the front heat exchanger are respectively connected with a high-pressure flash tank and a low-pressure flash tank; the expander is connected with a generator.
Further, the device also comprises a cooler; the inlet and outlet of the cooler are connected to the high-pressure flash tank and the low-pressure flash tank, respectively.
Furthermore, the inlet end and the outlet end of the cooler are respectively provided with a valve; and valves are respectively arranged at the inlet end and the outlet end of the first pipe of the front heat exchanger.
Furthermore, a hot water pump is connected in series in a loop of the hot water system; the hot water system is also connected with a constant-pressure water supplementing device.
Furthermore, a working medium pump is connected between the evaporator and the condenser in series.
Furthermore, a cooling water pump is connected in series in the condensation circulating system.
Further, the device also comprises a preheater; the first tube of the preheater is connected in series with the rear end of the first tube of the evaporator, and the second tube of the preheater is connected in series with the front end of the second tube of the evaporator.
Further, the system also comprises a heat regenerator; the heat regenerator is connected in parallel with the first tube of the condenser.
Furthermore, a bypass is arranged between the second pipe of the front heat exchanger and the first pipe of the evaporator; the bypass is provided with a regulating valve.
The invention has the beneficial effects that:
the invention has reasonable design and convenient control, can fully recover the waste heat of the black water flash steam, is applied to the power generation of the organic Rankine cycle system, effectively improves the utilization rate of energy and realizes the sustainable development of ecological environment.
Drawings
Fig. 1 is a schematic system structure diagram according to the first embodiment.
Fig. 2 is a schematic system structure diagram of the second embodiment.
Fig. 3 is a schematic structural diagram of the system according to the third embodiment.
FIG. 4 is a schematic structural diagram of a system according to a fourth embodiment.
Wherein: 1-high pressure flash tank; 2-valve I; 3-a cooler; 4-valve II; 5-valve III; 6-a pre-heat exchanger; 7-valve IV; 8-a hot water pump; 9-a constant pressure water replenishing device; 10-an evaporator; 11-a low-pressure flash tank; 12-a working medium pump; 13-an expander; 14-a generator; 15-a condenser; 16-a cooling water pump; 17-a cooling tower; 18-a preheater; 19-a heat regenerator; 20-bypass regulating valve. The arrows in the figure indicate the medium flow.
Detailed Description
The invention is further described below with reference to the figures and examples.
Embodiment one, as shown in fig. 1.
An organic Rankine cycle power generation system for recycling black water flash steam waste heat comprises a high-pressure flash tank 1, a cooler 3, a front heat exchanger 6, a constant-pressure water supplementing device 9, a low-pressure flash tank 11, an evaporator 10, an expansion machine 13, a power generator 14, a condenser 15 and a cooling tower 17.
An exhaust port of the expander 13 is connected with an air inlet of the expander 13 after sequentially passing through a first pipe of the condenser 15, the working medium pump 12 and a second pipe of the evaporator 10. Meanwhile, the expander 13 is connected to a generator 14 to form an organic rankine cycle system. The working medium in the organic Rankine cycle system can be selected from organic working media such as R134a and R245fa, so that high vapor pressure can be obtained under the low-temperature condition (80-300 ℃).
A second pipe of the condenser 15 is connected to a cooling tower 17 through a cooling water pump 16, and forms a condensation circulation system for cooling the exhaust gas of the expander 13.
The outlet of the first pipe of the evaporator 10 passes through the hot water pump 8 and the second pipe of the front heat exchanger 6, and then is connected to the inlet of the first pipe of the evaporator 10, so as to form a closed-loop hot water system. Meanwhile, the inlet and the outlet of the first pipe of the front heat exchanger 6 are respectively connected with the high-pressure flash tank 1 and the low-pressure flash tank 11. The waste heat of the high-pressure flash steam can be transferred to the working medium in the organic Rankine cycle system through the hot water system, so that the working medium is heated and then is supplied to the expansion machine to do work. The pressure water supplementing device is connected to the outlet end of the first pipe of the evaporator 10, so that the constant pressure can be performed on the hot water system, and the hot water is prevented from being vaporized when the temperature of the hot water exceeds 100 ℃. Simultaneously, can also carry out the moisturizing for hot water system. The hot water pump 8 is a power frequency pump. The constant pressure water supplementing device can adopt a full-film type air pressure constant pressure water supplementing device.
The high-pressure flash tank 1 is also connected with the low-pressure flash tank 11 after passing through the cooler 3. The inlet and the outlet of the cooler 3 are respectively provided with a valve I2 and a valve II4, and the inlet and the outlet of the first pipe of the front heat exchanger 6 are respectively provided with a valve III5 and a valve IV7, so that the flow direction of flash steam can be controlled, and favorable conditions are created for subsequent maintenance operation.
The cooler 3, the evaporator 10, the condenser 15 and the front heat exchanger 6 can adopt BEM type single-pass shell head-sealed tube box type heat exchangers.
The working process of the invention is as follows:
the waste heat of the black water flash steam is recovered through the front heat exchanger, the heat is transferred to the organic Rankine cycle system through the closed hot water system, the expansion machine is driven to work, and the generator is driven to generate power. The black water flash steam contains corrosive gas with certain components, and the front heat exchanger adopts corrosion-resistant stainless steel. The front heat exchanger and the cooler are arranged in parallel, and the operation of the cooler can be switched when the organic Rankine cycle generator set is overhauled and maintained. And during normal operation, the valve I and the valve II are closed, the valve III and the valve IV are opened, the black water flash steam enters the front heat exchanger after coming out of the high-pressure flash tank, and the condensed water after heat exchange enters the low-pressure flash tank again. The black water flash steam contains inflammable and explosive gas with certain components, the black water flash steam is isolated from the organic Rankine cycle system power generation system through the closed hot water system, and the organic Rankine cycle power generation system can be arranged in a non-explosion-proof area, so that the system cost is reduced. The hot water pump is controlled by adopting frequency conversion, the flow of the closed hot water system can be adjusted, the hot water flow can be adjusted according to the load fluctuation of the black water flash steam, and the organic Rankine cycle system is maintained to generate power under the optimal working condition. Organic working medium liquid enters the evaporator after being pressurized by the working medium pump, absorbs heat in the evaporator, the liquid is changed into gas, the gas pushes the expansion machine to do work, and the expansion machine drives the generator to generate electricity. And the organic working medium gas which does work is discharged from the expansion machine, enters the condenser to be cooled into liquid, and enters the working medium pump to complete the whole organic Rankine cycle. The cooling water exchanges heat with the organic working medium gas discharged by the expander in the condenser, and then the cooling water with increased temperature is cooled by the cooling tower and is cooled by the cooling water pump to complete the cooling circulation. The Rankine cycle power generation system expander adopts a turbine and has high power generation efficiency. When the Rankine cycle power generation system is overhauled and maintained, the valve I and the valve II are opened, the valve III and the valve IV are closed, the black water flash steam enters the cooler after coming out of the high-pressure flash tank, and the condensed water after heat exchange enters the low-pressure flash tank, so that the whole system can be maintained more conveniently.
Example two, as shown in fig. 2.
The second embodiment is basically the same as the first embodiment in structure, and the main difference is that: the second embodiment further includes a preheater 18. The first tube of the preheater 18 is connected in series to the rear end of the first tube of the evaporator 10, and the second tube thereof is connected in series to the front end of the second tube of the evaporator 10. When the organic working medium liquid expander operates, the organic working medium liquid is pressurized by the working medium pump and then enters the preheater for preheating, and then enters the evaporator for absorbing heat, so that the temperature of the organic working medium can be further increased, and the effect of the expander is improved.
Example three, as shown in fig. 3.
The third embodiment is basically the same as the first embodiment in structure, and the main difference is that: the third embodiment further includes a regenerator 19. The regenerator 19 is connected in parallel to the first tube of the condenser 15. When the organic working medium gas works, the organic working medium gas is discharged from the expansion machine, firstly enters the heat regenerator, and then enters the condenser to be cooled into liquid. In the heat regenerator, the waste heat of the exhaust gas of the expansion machine exchanges heat with the liquid organic working medium, so that the temperature of the organic working medium is increased, and the efficiency of the organic Rankine cycle system is improved.
Example four, as shown in fig. 4.
The fourth embodiment is basically the same as the first embodiment in structure, and the main difference is that: in the fourth embodiment, a bypass is provided between the second tube of the front heat exchanger 6 and the first tube of the evaporator 10, and the bypass is provided with the control valve 20. During operation, the regulation valve can be used for regulating the load fluctuation of the black water flash steam to regulate the flow of hot water and maintain the organic Rankine cycle system in the optimal power generation working condition.
The parts not involved in the present invention are the same as or can be implemented using the prior art.

Claims (9)

1. An organic Rankine cycle power generation system for recovering waste heat of black water flash steam comprises a Rankine cycle power generation system consisting of an expander, a generator, a condenser and an evaporator, and is characterized in that: an air outlet of the expander sequentially passes through a first pipe of the condenser and a second pipe of the evaporator and then is connected with an air inlet of the expander; a second pipe of the condenser is connected with the cooling tower in series to form a closed-loop condensation circulating system; the first pipe of the evaporator and the second pipe of the front heat exchanger are connected in series to form a closed-loop hot water system; the inlet and the outlet of the first pipe of the front heat exchanger are respectively connected with a high-pressure flash tank and a low-pressure flash tank; the expander is connected with a generator.
2. The organic Rankine cycle power generation system for recovering waste heat of black water flash steam according to claim 1, wherein: also includes a cooler; the inlet and outlet of the cooler are connected to the high-pressure flash tank and the low-pressure flash tank, respectively.
3. The organic Rankine cycle power generation system for recovering waste heat of black water flash steam according to claim 2, wherein: the inlet end and the outlet end of the cooler are respectively provided with a valve; and valves are respectively arranged at the inlet end and the outlet end of the first pipe of the front heat exchanger.
4. The organic Rankine cycle power generation system for recovering waste heat of black water flash steam according to claim 1, wherein: a hot water pump is connected in series in a loop of the hot water system; the hot water system is also connected with a constant-pressure water supplementing device.
5. The organic Rankine cycle power generation system for recovering waste heat of black water flash steam according to claim 1, wherein: and a working medium pump is connected between the evaporator and the condenser in series.
6. The organic Rankine cycle power generation system for recovering waste heat of black water flash steam according to claim 1, wherein: and a cooling water pump is connected in series in the condensation circulating system.
7. The organic Rankine cycle power generation system for recovering waste heat of black water flash steam according to claim 1, wherein: the device also comprises a preheater; the first tube of the preheater is connected in series with the rear end of the first tube of the evaporator, and the second tube of the preheater is connected in series with the front end of the second tube of the evaporator.
8. The organic Rankine cycle power generation system for recovering waste heat of black water flash steam according to claim 1, wherein: the system also comprises a heat regenerator; the heat regenerator is connected in parallel with the first tube of the condenser.
9. The organic Rankine cycle power generation system for recovering waste heat of black water flash steam according to claim 1, wherein: a bypass is arranged between the second pipe of the front heat exchanger and the first pipe of the evaporator; the bypass is provided with a regulating valve.
CN202010260879.9A 2020-04-03 2020-04-03 Organic Rankine cycle power generation system for recycling black water flash steam waste heat Pending CN111287817A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010260879.9A CN111287817A (en) 2020-04-03 2020-04-03 Organic Rankine cycle power generation system for recycling black water flash steam waste heat

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010260879.9A CN111287817A (en) 2020-04-03 2020-04-03 Organic Rankine cycle power generation system for recycling black water flash steam waste heat

Publications (1)

Publication Number Publication Date
CN111287817A true CN111287817A (en) 2020-06-16

Family

ID=71019475

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010260879.9A Pending CN111287817A (en) 2020-04-03 2020-04-03 Organic Rankine cycle power generation system for recycling black water flash steam waste heat

Country Status (1)

Country Link
CN (1) CN111287817A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111594280A (en) * 2020-06-23 2020-08-28 南京天加热能技术有限公司 Double-turbine gas suspension ORC power generation system and control method
CN111594283A (en) * 2020-06-23 2020-08-28 南京天加热能技术有限公司 Two-stage turbine gas suspension ORC power generation system and control method

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2514931A1 (en) * 2011-04-20 2012-10-24 General Electric Company Integration of waste heat from charge air cooling into a cascaded organic rankine cycle system
CN203132371U (en) * 2013-03-26 2013-08-14 哈尔滨广瀚新能动力有限公司 Lime kiln flue gas waste heat recovery power generation system based on organic Rankine cycle
CN107158891A (en) * 2017-05-22 2017-09-15 中国成达工程有限公司 A kind of coal gasified black water flashed vapour utilizes technique
CN107840515A (en) * 2017-11-24 2018-03-27 航天长征化学工程股份有限公司 Slag and grey water treatment system
CN108167027A (en) * 2017-12-27 2018-06-15 山西晋城无烟煤矿业集团有限责任公司 Pressurized gasification chilling process vacuum flash vapour electricity-generating method
CN110593973A (en) * 2019-09-01 2019-12-20 天津大学 System for improving power generation capacity through organic Rankine cycle combined with flash evaporation and control method
CN110877919A (en) * 2018-12-27 2020-03-13 宁夏神耀科技有限责任公司 Coal gasification black water heat recovery method and device
CN211950617U (en) * 2020-04-03 2020-11-17 南京天加热能技术有限公司 Organic Rankine cycle power generation system for recycling black water flash steam waste heat

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2514931A1 (en) * 2011-04-20 2012-10-24 General Electric Company Integration of waste heat from charge air cooling into a cascaded organic rankine cycle system
CN203132371U (en) * 2013-03-26 2013-08-14 哈尔滨广瀚新能动力有限公司 Lime kiln flue gas waste heat recovery power generation system based on organic Rankine cycle
CN107158891A (en) * 2017-05-22 2017-09-15 中国成达工程有限公司 A kind of coal gasified black water flashed vapour utilizes technique
CN107840515A (en) * 2017-11-24 2018-03-27 航天长征化学工程股份有限公司 Slag and grey water treatment system
CN108167027A (en) * 2017-12-27 2018-06-15 山西晋城无烟煤矿业集团有限责任公司 Pressurized gasification chilling process vacuum flash vapour electricity-generating method
CN110877919A (en) * 2018-12-27 2020-03-13 宁夏神耀科技有限责任公司 Coal gasification black water heat recovery method and device
CN110593973A (en) * 2019-09-01 2019-12-20 天津大学 System for improving power generation capacity through organic Rankine cycle combined with flash evaporation and control method
CN211950617U (en) * 2020-04-03 2020-11-17 南京天加热能技术有限公司 Organic Rankine cycle power generation system for recycling black water flash steam waste heat

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111594280A (en) * 2020-06-23 2020-08-28 南京天加热能技术有限公司 Double-turbine gas suspension ORC power generation system and control method
CN111594283A (en) * 2020-06-23 2020-08-28 南京天加热能技术有限公司 Two-stage turbine gas suspension ORC power generation system and control method
CN111594280B (en) * 2020-06-23 2023-09-19 南京天加能源科技有限公司 Dual-turbine gas suspension ORC power generation system and control method

Similar Documents

Publication Publication Date Title
CN111022138B (en) Supercritical carbon dioxide power generation system based on absorption heat pump waste heat recovery
CN108561282B (en) Trough type direct steam and molten salt combined thermal power generation system
CN108005744B (en) Supercritical CO 2 Circulating machine furnace cold energy recovery and power generation integrated heat supply method
CN103967648A (en) Comprehensive waste heat recovery system of ship low-speed diesel engine
CN107941028B (en) Sintering cooling waste gas waste heat power generation system with organic Rankine cycle
CN113586185B (en) Coal-fired boiler flue gas and steam combined heat storage deep peak regulation system and operation method
CN104832232A (en) Gradient heat exchange organic Rankine cycle power generation system and power generation method thereof
CN203201684U (en) Internal combustion engine generator set waste heat cascade recycling system based on Rankine cycle
CN110173347A (en) A kind of waste heat recycling system and operation method of coal mine equipment in use
CN104457297B (en) A kind of sintering waste heat recovery method and system
CN111287817A (en) Organic Rankine cycle power generation system for recycling black water flash steam waste heat
CN111075521B (en) High-low pressure double working medium ORC power generation system with regenerative cycle
CN210237656U (en) Power generation device for recycling waste heat of blast furnace slag flushing water
CN211950617U (en) Organic Rankine cycle power generation system for recycling black water flash steam waste heat
CN207730035U (en) Sintering with Organic Rankine Cycle cools down power generation system using waste heat
CN112833382A (en) Multi-stage waste heat comprehensive utilization device and method for power plant
CN204404812U (en) A kind of sintering waste heat recovery system
CN114776411B (en) Integrated heat storage coal-fired power generation system and working method
CN211950616U (en) Organic Rankine cycle power generation system capable of directly recycling black water waste heat
CN113899006B (en) Heating system for driving heat pump to recover circulating water waste heat by utilizing low-pressure heater and drainage water
CN115750004A (en) Residual pressure waste heat recovery power receiving and transmitting system and residual pressure waste heat recovery method
CN109356724B (en) Coupling method of flue gas waste heat supply and air inlet cooling and gas heating
CN212563346U (en) Polyester esterification steam waste heat power generation system
CN213478412U (en) Liquid oxygen cold energy power generation system
CN111287816A (en) Organic Rankine cycle power generation system capable of directly recycling black water waste heat

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination