CN106076315A - A kind of vanadium molybdenum composite oxides low-temperature denitration catalyst and preparation method thereof - Google Patents

A kind of vanadium molybdenum composite oxides low-temperature denitration catalyst and preparation method thereof Download PDF

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Publication number
CN106076315A
CN106076315A CN201610460271.4A CN201610460271A CN106076315A CN 106076315 A CN106076315 A CN 106076315A CN 201610460271 A CN201610460271 A CN 201610460271A CN 106076315 A CN106076315 A CN 106076315A
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temperature
composite oxides
denitration catalyst
catalyst
vanadium
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Inventor
赵建新
钱军
陈玲
孟德海
孙志翱
高宽峰
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WUXI HUAGUANG NEW POWER ENVIRONMENTAL PROTECTION TECHNOLOGY Co Ltd
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WUXI HUAGUANG NEW POWER ENVIRONMENTAL PROTECTION TECHNOLOGY Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24Chromium, molybdenum or tungsten
    • B01J23/28Molybdenum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8621Removing nitrogen compounds
    • B01D53/8625Nitrogen oxides
    • B01D53/8628Processes characterised by a specific catalyst
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/90Injecting reactants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/40Mixed oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts

Abstract

The invention provides a kind of vanadium molybdenum composite oxides low-temperature denitration catalyst, after it can be disposed at cleaner unit and desulfurizer, thus effectively reduce flying dust and the impact of sulfur content in flue gas, and the selective catalytic reduction reaction of the nitrogen oxides that may be adapted under cryogenic conditions in boiler smoke, there is preferable denitration efficiency, it addition, present invention also offers the preparation method of a kind of vanadium molybdenum composite oxides low-temperature denitration catalyst;It includes Nano titanium dioxide, water, Bronsted acid, emprotid, plasticizer, pore creating material, reinforcing agent, lubricant, and is to add vanadic salts and molybdenum salt after 1:0.1 ~ 1:0.02 ~ 0.2:0.05 ~ 0.5:0.005 ~ 0.02:0.005 ~ 0.02:0.05 ~ 0.3:0.005 ~ 0.02 mix homogeneously according to the mass ratio between each component.

Description

A kind of vanadium molybdenum composite oxides low-temperature denitration catalyst and preparation method thereof
Technical field
The present invention relates to the technical field of denitrating catalyst and manufacture thereof, be specially a kind of vanadium molybdenum composite oxides low temperature and take off Denox catalyst and preparation method thereof.
Background technology
Selective catalytic reduction (SCR) gas denitrifying technology is as the control coal-burning power plant nitrogen oxides row generally acknowledged at present Putting most efficient method, be widely used in coal-burning power plant of China, the technological core of SCR flue-gas denitration process is denitration catalyst Agent, currently used denitrating catalyst the most ripe, most commonly used is vanadium tungsten Titanium series catalyst, general operation temperature 300 ~ 400 DEG C, before denitrating catalyst is typically located at cleaner unit, but due in flue gas fly ash content higher, easily catalyst is made Becoming abrasion, catalyst life is shorter, general the most available 3 years, and meanwhile, the impurity such as the alkali metal oxide contained in flying dust can make Catalyst poisoning lost efficacy, and sulfureous in flue gas content is higher, and denitrating catalyst can be by part SO2It is oxidized to SO3, SO3With escape NH3Easily reaction forms sulfur ammonium, thus causes the corrosion of upstream device, then in order to reduce flying dust and the shadow of sulfur content in flue gas Ringing, after denitrating catalyst is arranged in cleaner unit and desulfurizer, its temperature reduces, about at 120 ~ 250 DEG C, almost without flying Ash impact, but after flue gas is by cleaner unit and desulfurizer, significantly reducing of temperature, the denitration of existing routine can be caused to urge Agent cannot directly use, and denitration efficiency is the highest.
Summary of the invention
For the problems referred to above, the invention provides a kind of vanadium molybdenum composite oxides low-temperature denitration catalyst, it can be disposed at After cleaner unit and desulfurizer, thus effectively reduce flying dust and the impact of sulfur content in flue gas, and may be adapted under cryogenic conditions The selective catalytic reduction reaction of the nitrogen oxides in boiler smoke, has preferable denitration efficiency, it addition, the present invention also provides for A kind of preparation method of vanadium molybdenum composite oxides low-temperature denitration catalyst.
A kind of vanadium molybdenum composite oxides low-temperature denitration catalyst, it is characterised in that: it include Nano titanium dioxide, water, Bronsted acid, emprotid, plasticizer, pore creating material, reinforcing agent, lubricant, and be 1: 0.1 ~ 1 according to the mass ratio between each component : 0.02 ~ 0.2: 0.05 ~ 0.5: 0.005 ~ 0.02: 0.005 ~ 0.02: 0.05 ~ 0.3: 0.005 ~ 0.02 mixing is all Vanadic salts and molybdenum salt is added after even.
It is further characterized by described vanadic salts, molybdenum salt addition true according to the quality of described Nano titanium dioxide Fixed, described Nano titanium dioxide: vanadic salts: the mass ratio between molybdenum salt is 1: 0.0342 ~ 0.0855:0.0513 ~ 0.171;
Described Bronsted acid uses acetic acid or lactic acid;Described emprotid uses ammonia or ethanolamine;Described plasticizer uses CMC Or PEO or CMC mixing PEO;Described pore creating material uses purified cotton or activated carbon;Described reinforcing agent uses glass or carbon Fiber;Described lubricant uses stearic acid or glycerol;Described vanadic salts uses ammonium metavanadate or vanadyl oxalate;Described molybdenum salt Use ammonium paramolybdate or acetic acid molybdenum;
Described plasticizer uses CMC mixing PEO's, and described mass ratio between CMC, PEO is 1: 2 ~ 5.
A kind of preparation method of vanadium molybdenum composite oxides low-temperature denitration catalyst, it is characterised in that: its preparation process is,
(1), mixing action: by Nano titanium dioxide, water, Bronsted acid, emprotid, plasticizer, pore creating material, reinforcing agent, lubrication Agent according to mass ratio 1: 0.1 ~ 1: 0.02 ~ 0.2: 0.05 ~ 0.5: 0.005 ~ 0.02: 0.005 ~ 0.02: 0.05 ~ 0.3: 0.005 ~ 0.02 by adding vanadic salts and molybdenum salt formation plastic mud material after mixing method mix homogeneously;
(2), once ageing: the plastic mud material obtained in described step (1) moisturizing ageing under 25 DEG C of constant temperature is placed 1 day ~ 2 My god;
(3), pre-extruded: the plastic mud material pre-extruded equipment obtained in described step (2) is carried out pre-extruded operation, forms mud Material square;
(4), secondary ageing: the pug square obtained in described step (3) moisturizing ageing under 25 DEG C of constant temperature is placed 1 day ~ 2 My god;
(5), extrusion molding: the pug square extrusion equipment obtained in described step (4) is carried out extrusion operation, obtains honeycomb Shape sample;
(6), primary drying: the cellular sample obtained in described step (5) stagewise temperature programming at 30 ~ 70 DEG C is dried Catalyst, drying time is 5 days ~ 8 days;
(7), redrying: the cellular sample obtained in described step (6) stagewise temperature programming at 100 ~ 300 DEG C is done Dry catalyst, drying time is 3 h ~ 5h;
(8), high-temperature roasting: the cellular sample roasting 3 h ~ 8h under 400 ~ 600 DEG C of high temperature that will obtain in described step (7), Thus obtain vanadium molybdenum composite oxides low-temperature denitration catalyst.
The invention has the beneficial effects as follows, by the vanadium molybdenum composite oxides low-temperature denitration catalyst of preparation so that denitration is urged After agent can be arranged in cleaner unit and desulfurizer, thus in flue gas flying dust and the impact of sulfur content are greatly reduced, and can The selective catalytic reduction reaction of the nitrogen oxides being effectively adapted under cryogenic conditions in boiler smoke, has preferable denitration effect Rate, decreases the Poisoning Effect to catalyst such as sulfureous in flue gas content, largely due to applied environment (low dirt ring simultaneously Border) it is better than conventional denitrating catalyst, service life is longer, and total cost of investment reduces.
Detailed description of the invention
Embodiment one
Prepared by catalyst:
(1), mixing action: by Nano titanium dioxide, water, lactic acid, ammonia, PEO, purified cotton, glass, stearic acid according to quality Than 1: 0.1: 0.02: 0.05: 0.005: 0.005: 0.05: 0.005 by adding after mixing method mix homogeneously Entering ammonium metavanadate and ammonium paramolybdate forms plastic mud material, the addition of ammonium metavanadate and ammonium paramolybdate is according to Nano titanium dioxide Quality determine, specifically Nano titanium dioxide: ammonium metavanadate: between ammonium paramolybdate, mass ratio is 1: 0.0342: 0.0513;
(2), once ageing: the plastic mud material obtained in described step (1) moisturizing ageing under 25 DEG C of constant temperature is placed 1 day;
(3), pre-extruded: the plastic mud material pre-extruded equipment obtained in described step (2) is carried out pre-extruded operation, forms mud Material square;
(4), secondary ageing: the pug square obtained in described step (3) moisturizing ageing under 25 DEG C of constant temperature is placed 1 day;
(5), extrusion molding: the pug square extrusion equipment obtained in described step (4) is carried out extrusion operation, obtains honeycomb Shape sample;
(6), primary drying: the cellular sample obtained in step (5) stagewise temperature programming at 30 ~ 70 DEG C is dried catalysis Agent, i.e. temperature are dried 1 day when 30 DEG C, and temperature is dried 1 day when 40 DEG C, and temperature is dried 1 day when 50 DEG C, and temperature is when 60 DEG C Be dried 1 day, temperature be dried when 70 DEG C 1 day to constant weight, drying time is 5 days altogether;
(7), redrying: the cellular sample stagewise temperature programming at 100 ~ 300 DEG C completing step (6) is dried catalysis Agent, i.e. temperature are dried 1h when 100 DEG C, and temperature is dried 2h when 300 DEG C, and drying time is 3h;
(8), high-temperature roasting: cellular sample roasting 8h under 400 DEG C of high temperature of step (7) will be completed, i.e. can get vanadium molybdenum multiple Close oxide low-temperature denitration catalyst.
Catalyst activity is tested:
Activity experiment is carried out on fixed bed reactors, is 6 × 6 holes, length 20cm by the loaded catalyst completed Catalyst sample, and at NH3/ NO mol ratio is 1, O2Concentration is 5%, air speed is 7500h-1Flue gas condition under, reaction temperature is When 160 DEG C, denitration efficiency is 28.56%;When reaction temperature is 220 DEG C, denitration efficiency is 67.24%.
Embodiment two
Prepared by catalyst:
(1), mixing action: by Nano titanium dioxide, water, acetic acid, ethanolamine, CMC, purified cotton, glass, stearic acid according to matter Amount is more inclined by adding after mixing method mix homogeneously than 1: 0.5: 0.1: 0.1: 0.01: 0.01: 0.1: 0.01 Ammonium vanadate and ammonium paramolybdate form plastic mud material, and the addition of ammonium metavanadate and ammonium paramolybdate is true according to the quality of titanium dioxide Fixed, specifically Nano titanium dioxide: ammonium metavanadate: the mass ratio between ammonium paramolybdate is 1: 0.06: 0.1;
(2), once ageing: the plastic mud material obtained in step (1) moisturizing ageing under 25 DEG C of constant temperature is placed 2 days;
(3), pre-extruded: the plastic mud material pre-extruded equipment completing step (2) is carried out pre-extruded operation, forms pug side Block;
(4), secondary ageing: the pug square obtained in step (3) moisturizing ageing under 25 DEG C of constant temperature is placed 2 days;
(5), extrusion molding: the pug square extrusion equipment completing step (4) is carried out extrusion operation, obtains cellular sample Product;
(6), primary drying: the cellular sample obtained in step (5) stagewise temperature programming at 30 ~ 70 DEG C is dried catalysis Agent, i.e. temperature are dried 1 day when 30 DEG C, and temperature is dried 1 day when 40 DEG C, and temperature is dried 1 day when 50 DEG C, and temperature is when 60 DEG C Being dried 1 day, temperature is dried 1 day when 70 DEG C, constant weight 1 day, and drying time is 6 days;
(7), redrying: the cellular sample stagewise temperature programming at 100 ~ 300 DEG C completing step (6) is dried catalysis Agent, i.e. temperature be 2h when 100 DEG C, and temperature is 3h when 300 DEG C, and drying time is 5h;
(8), high-temperature roasting: cellular sample roasting 5h under 600 DEG C of high temperature of step (7) will be completed, i.e. can get vanadium molybdenum multiple Close oxide low-temperature denitration catalyst.
Catalyst activity is tested:
Under flue gas condition with embodiment one, when reaction temperature is 160 DEG C, denitration efficiency is 35.54%;Reaction temperature is 220 DEG C Time, denitration efficiency is 80.31%.
Embodiment three
Prepared by catalyst:
(1), mixing action: by Nano titanium dioxide, water, lactic acid, ammonia, CMC, activated carbon, glass, glycerol according to quality Than 1: 0.8: 0.15: 0.2: 0.015: 0.015: 0.2: 0.01 by adding grass after mixing method mix homogeneously Acid vanadyl and acetic acid molybdenum form plastic mud material, and the addition of vanadyl oxalate and acetic acid molybdenum determines according to the quality of titanium dioxide, tool Body ground Nano titanium dioxide: vanadyl oxalate: the mass ratio between acetic acid molybdenum is 1: 0.0855: 0.171;
(2), once ageing: the plastic mud material obtained in step (1) moisturizing ageing under 25 DEG C of constant temperature is placed 1 day;
(3), pre-extruded: the plastic mud material pre-extruded equipment completing step (2) is carried out pre-extruded operation, forms pug side Block;
(4), secondary ageing: the pug square obtained in step (3) moisturizing ageing under 25 DEG C of constant temperature is placed 1 day;
(5), extrusion molding: the pug square extrusion equipment completing step (4) is carried out extrusion operation, obtains cellular sample Product;
(6), primary drying: the cellular sample obtained in step (5) stagewise temperature programming at 30 ~ 70 DEG C is dried catalysis Agent, i.e. temperature are dried 1 day when 30 DEG C, and temperature is dried 1 day when 40 DEG C, and temperature is dried 1 day when 50 DEG C, and temperature is when 60 DEG C Being dried 1 day, temperature is dried 1 day when 70 DEG C, constant weight 2 days, and drying time is 7 days;
(7), redrying: the cellular sample stagewise temperature programming at 100 ~ 300 DEG C completing step (6) is dried catalysis Agent, i.e. temperature be 1h when 100 DEG C, and temperature is 3h when 300 DEG C, and drying time is 4h;
(8), high-temperature roasting: cellular sample roasting 6h under 500 DEG C of high temperature of step (7) will be completed, i.e. can get vanadium molybdenum multiple Close oxide low-temperature denitration catalyst.
Catalyst activity is tested:
Under flue gas condition with embodiment one, when reaction temperature is 160 DEG C, denitration efficiency is 30.83%;Reaction temperature is 220 DEG C Time, denitration efficiency is 65.92%.
To sum up, above-mentioned mixing method preparation technology is used, it is simple to realize the work of vanadium molybdenum composite oxides low-temperature denitration catalyst Industry metaplasia is produced, and catalyst performance aspect, in the range of said components, is tested by catalyst activity, by Catalyst packing in solid Carrying out catalyst denitration activity detection on fixed bed reactor, in the range of 130 ~ 280 DEG C, the highest denitration efficiency is 80.31%, there is preferable practicality.

Claims (5)

1. a vanadium molybdenum composite oxides low-temperature denitration catalyst, it is characterised in that: it includes Nano titanium dioxide, water, matter Son acid, emprotid, plasticizer, pore creating material, reinforcing agent, lubricant, and be 1: 0.1 ~ 1 according to the mass ratio between each component: 0.02 ~ 0.2: 0.05 ~ 0.5: 0.005 ~ 0.02: 0.005 ~ 0.02: 0.05 ~ 0.3: 0.005 ~ 0.02 mix homogeneously Rear addition vanadic salts and molybdenum salt.
A kind of vanadium molybdenum composite oxides low-temperature denitration catalyst the most according to claim 1, it is characterised in that: described vanadium Salt, the addition of molybdenum salt determine according to the quality of described Nano titanium dioxide, described Nano titanium dioxide: vanadic salts: molybdenum salt Between mass ratio be 1: 0.0342 ~ 0.0855:0.0513 ~ 0.171.
A kind of vanadium molybdenum composite oxides low-temperature denitration catalyst the most according to claim 1, it is characterised in that: described proton Acid uses acetic acid or lactic acid;Described emprotid uses ammonia or ethanolamine;Described plasticizer use CMC or PEO or CMC mixing PEO;Described pore creating material uses purified cotton or activated carbon;Described reinforcing agent uses glass or carbon fiber;Described profit Lubrication prescription uses stearic acid or glycerol;Described vanadic salts uses ammonium metavanadate or vanadyl oxalate;Described molybdenum salt uses para-molybdic acid Ammonium or acetic acid molybdenum.
A kind of vanadium molybdenum composite oxides low-temperature denitration catalyst the most according to claim 3, it is characterised in that: described plasticising Agent uses CMC mixing PEO's, and described mass ratio between CMC, PEO is 1: 2 ~ 5.
5. use the preparation method of vanadium molybdenum composite oxides low-temperature denitration catalyst as claimed in claim 1, it is characterised in that: Its preparation process is,
(1), mixing action: by Nano titanium dioxide, water, Bronsted acid, emprotid, plasticizer, pore creating material, reinforcing agent, lubrication Agent according to mass ratio 1: 0.1 ~ 1: 0.02 ~ 0.2: 0.05 ~ 0.5: 0.005 ~ 0.02: 0.005 ~ 0.02: 0.05 ~ 0.3: 0.005 ~ 0.02 by adding vanadic salts and molybdenum salt formation plastic mud material after mixing method mix homogeneously;
(2), once ageing: the plastic mud material obtained in described step (1) moisturizing ageing under 25 DEG C of constant temperature is placed 1 day ~ 2 My god;
(3), pre-extruded: the plastic mud material pre-extruded equipment obtained in described step (2) is carried out pre-extruded operation, forms mud Material square;
(4), secondary ageing: the pug square obtained in described step (3) moisturizing ageing under 25 DEG C of constant temperature is placed 1 day ~ 2 My god;
(5), extrusion molding: the pug square extrusion equipment obtained in described step (4) is carried out extrusion operation, obtains honeycomb Shape sample;
(6), primary drying: the cellular sample obtained in described step (5) stagewise temperature programming at 30 ~ 70 DEG C is dried Catalyst, drying time is 5 days ~ 8 days;
(7), redrying: the cellular sample obtained in described step (6) stagewise temperature programming at 100 ~ 300 DEG C is done Dry catalyst, drying time is 3 h ~ 5h;
(8), high-temperature roasting: the cellular sample roasting 3 h ~ 8h under 400 ~ 600 DEG C of high temperature that will obtain in described step (7), Thus obtain vanadium molybdenum composite oxides low-temperature denitration catalyst.
CN201610460271.4A 2016-06-23 2016-06-23 A kind of vanadium molybdenum composite oxides low-temperature denitration catalyst and preparation method thereof Pending CN106076315A (en)

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Cited By (2)

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CN111530449A (en) * 2020-06-09 2020-08-14 江苏龙净科杰环保技术有限公司 Wall-flow dedusting low-temperature denitration honeycomb catalyst for flue gas and preparation process thereof
CN113655170A (en) * 2021-08-04 2021-11-16 安徽迪诺环保新材料科技有限公司 Method for measuring denitration rate of nano titanium dioxide powder for flue gas denitration catalyst

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CN103170344A (en) * 2011-12-23 2013-06-26 李雪梅 Catalyst for low-temperature SCR (Selective Catalytic Reduction) denitration and preparation method of catalyst
CN105126824A (en) * 2015-08-21 2015-12-09 无锡华光新动力环保科技股份有限公司 Low-temperature manganese-based composite oxide denitration catalyst and preparation method thereof

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CN111530449A (en) * 2020-06-09 2020-08-14 江苏龙净科杰环保技术有限公司 Wall-flow dedusting low-temperature denitration honeycomb catalyst for flue gas and preparation process thereof
CN111530449B (en) * 2020-06-09 2021-08-10 江苏龙净科杰环保技术有限公司 Wall-flow dedusting low-temperature denitration honeycomb catalyst for flue gas and preparation process thereof
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CN113655170A (en) * 2021-08-04 2021-11-16 安徽迪诺环保新材料科技有限公司 Method for measuring denitration rate of nano titanium dioxide powder for flue gas denitration catalyst

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Application publication date: 20161109