CN104479794B - A kind of fusing assistant and using method thereof reducing gasified pulverized coal slag ash fusion point temperature - Google Patents

A kind of fusing assistant and using method thereof reducing gasified pulverized coal slag ash fusion point temperature Download PDF

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CN104479794B
CN104479794B CN201410577199.4A CN201410577199A CN104479794B CN 104479794 B CN104479794 B CN 104479794B CN 201410577199 A CN201410577199 A CN 201410577199A CN 104479794 B CN104479794 B CN 104479794B
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fusing assistant
coal
ash
paper mill
mill sludge
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CN104479794A (en
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马菊梅
周棋
毛宇
刘泰生
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Dongfang Boiler Group Co Ltd
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Abstract

The invention discloses a kind of fusing assistant and the using method thereof that reduce gasified pulverized coal slag ash fusion point temperature, belong to fusing assistant field, described fusing assistant is paper mill sludge, described paper mill sludge contains organism, empty butt thermal value is 800 kilocalories/kg ~ 1000 kilocalorie/kg, basic oxide mass content more than 50%, do are its chemical composition and mass content thereof: CaO? 40% ~ 56%, MgO? 3% ~ 12%, Al 2o 33% ~ 12%, Fe 2o 39% ~ 15%, SiO 214% ~ 20%, SO 3< 3%, TiO 2< 0.8%, and mass content is the alkalimetal oxide of less than 1% and a small amount of impurity.Using method, when the texturing temperature less than 1450 DEG C of feed coal, the add-on 6% ~ 15% of fusing assistant, higher than 1450 DEG C, addition is between 15% ~ 30%.The present invention both can reduce coal ash fusion temperature effectively, achieved again the utilization of waste as resource of paper mill sludge, make use of again the heat of paper mill sludge simultaneously.

Description

A kind of fusing assistant and using method thereof reducing gasified pulverized coal slag ash fusion point temperature
Technical field
The invention belongs to fusing assistant field.
Background technology
Current entrained flow bed gasification technology has become both at home and abroad on a large scale, the one preferred technique of high-level efficiency gasification, its deslagging mode mainly slag tap.Slag tap requires that the yield temperature of ash is less than 1400 DEG C, and ash fusion point is too high, can reduce refractory life, normally runs bring many problems to device.Rich coal resources in China, has a large amount of coal to be high-ash-fusion coal.Also slag tap gasifying process can be applied in order to make high-ash-fusion coal, generally by add fusing assistant that economy is easy to get or with the low coal of coal ash melting temperature with certain proportion with the use of reducing grey melt temperature, wherein, the fusing assistant that interpolation economy is easy to get can be considered one of cost-effective feasible measure.
The current vapourizing furnace method of adding non-flammable Wingdale that adopts reduces coal ash fusion temperature more, but Wingdale interpolation is excessive easily causes stifled slag.As an alternative, the fusing assistant reducing coal ash has investigator and has carried out large quantity research, there are the fusing assistants such as calcium base, iron-based, magnesium base and sodium base, add the various pure compound, mixture, ore etc. being rich in basic oxide such as basic oxide ore powder as fusing assistant.Being added on of these fusing assistants can reduce coal fusion point of ash in varying degrees effectively.If publication number is the patent of invention that CN1970698 discloses " a kind of fusing assistant reducing coal ash fusion temperature and preparation method thereof ", fusing assistant described in it is that described fusing assistant has following component (% by weight): CaCO for reducing producing the ash fusion point of lime-ash in coal gasification course and the additive added in coal 382% ~ 93%; Fe 2o 32% ~ 16%, surplus is MgCO 3.This fusing assistant is evenly mixed in coal, can change its ash melting characteristic in gasification, reduces ash fusion point and ash viscosity, thus lime-ash is discharged in liquid form smoothly.For another example publication number is that CN102304409A discloses " a kind of fusing assistant improving gasified pulverized coal slag melting ", it adopts the straw ash being rich in basic oxide as solubility promoter, and the composition of described straw ash fusing assistant and content are the alkalimetal oxide,>=SiO of 23.48% of 5.00% ~ 40% by important ratio 2the TiO of ,≤2.63% 2the Fe of ,≤14.14% 2o 3the CaO of,>=1.34%, surplus are MgO.Its fusing assistant has two typical characteristics: one is have higher silica/alumina ratio: 7.00 ~ 80.00; Two is that the content of alkalimetal oxide is higher: 5.00% ~ 40.00%.This fusing assistant can improve the characteristic of gasified pulverized coal slag melting, reduces coal ash fusion temperature.For another example publication number is that 101665737A discloses " a kind of efficient composite fluxing agent improving melting characteristic of gasified pulverized coal slag ", this efficient composite fluxing agent contains basic oxide ore powder by two or more and is composited, i.e. content of MgO 12% ~ 30%, CaO content 3% ~ 30% in fusing assistant.For Wan Bei mining area coal, when addition is 2% ~ 6%, coal ash melting temperature can be made to be reduced to less than 1400 DEG C from 1500 DEG C, viscosity is within the scope of 2 ~ 25PaS, effective melting characteristic improving Wan Bei mining area coal, this fusing assistant can be used for alternative limestone flux, and addition is only the half of Wingdale.
Paper mill sludge is that a large amount of wastes produced in various paper product process are being manufactured in paper mill, refer to throw out, particulate matter and the floating matter with producing after the process waste water such as Physical, chemical method, physico-chemical processes and biological process, paper mill sludge is the end product of wastewater treatment in pulping and papermaking processes.According to Chinese papermaking association statistics, Chinese paper in 2010 and cardboard ultimate production 9,270 ten thousand tons, consumption 9,173 ten thousand tons, the residue that the whole industry produces wets about 900 ~ 1,000 ten thousand tons, mud.Along with production and the rapid development of economy of China's paper industry, the quantity of papermaking enterprise increases year by year, and scale is increasing, and the generation of paper mill sludge also increases sharply.The treatment process of China to paper mill sludge has landfill, compost and burning.Current mode disposed its process, mainly based on landfill, only has part to be fully utilized, not only wastes a large amount of land resources, but also can produce secondary pollution.
Summary of the invention
The object of the invention is to: propose a kind of fusing assistant and the using method thereof that reduce gasified pulverized coal slag ash fusion point temperature, using paper mill sludge as fusing assistant, both effectively coal ash fusion temperature can be reduced, high-ash-fusion coal is made also to go for slag tap vapourizing furnace, widen the use range of high-ash-fusion coal, add the Suitability of Coals of slag tap vapourizing furnace, achieve again the utilization of waste as resource of paper mill sludge, make use of again the heat of paper mill sludge simultaneously, reach the object of economizing on coal, killing three birds with one stone; Meanwhile, this solubility promoter adopts less consumption can reduce ash fusion point temperature significantly, and to addition unrestriction.
The chemical composition of coal ash is very complicated, and mainly salt and various metal and nonmetal oxide, mainly contain silicon-dioxide (SiO 2), alchlor (Al 2o 3), ferric oxide (Fe 2o 3), calcium oxide (CaO), magnesium oxide (MgO), manganese oxide (MnO), titanium dioxide (TiO 2), Vanadium Pentoxide in FLAKES (P 2o 5), sulphur trioxide (SO 3), potassium oxide (K 2o), sodium oxide (Na 2o) etc.According to the ionic potential of metal ion in coal ash chemical composition, oxide compound can be divided into two large classes, i.e. basic oxide (Fe 2o 3, MgO, CaO, Na 2o, K 2and acidic oxide (SiO O) 2, Al 2o 3, TiO 2).Atmosphere one timing residing for coal ash, have certain relation between ash fusion point and components of coal ash, when typically in ash, the content of acidic oxide is greater than basic oxide content, coal ash melting temperature is higher; On the contrary, coal ash melting temperature is lower.
Therefore, all utilize various basic oxide and composition thereof as solubility promoter in prior art, but the problem that prior art never solves is: be conducive to reducing ash fusion point as solubility promoter although typically add basic oxide, but add which kind of basic oxide and composition thereof, and the basic oxide mixture of which kind of proportions, and even basic oxide and other materials how compound, can with minimum addition, realize maximum ash fusion point temperature to reduce? conclusion is never had: various solubility promoters as mentioned in the background in prior art, its composition is similar, but result differs very large, co-solvent components, have no rule between proportioning and reduction ash fusion point temperature effect can say.
And, also there is a problem in the solubility promoter of prior art: typically, solubility promoter addition is larger, and ash fusion point temperature decline degree is larger, therefore, for the raw coal that some ash fusion point temperature is higher, usually need the solubility promoter adding more amount, but solubility promoter not again The more the better, such as the most frequently used Wingdale, after addition reaches certain proportion, on the contrary along with the interpolation of Wingdale, ash fusion point temperature significantly promotes.Therefore, in prior art, the interpolation of solubility promoter is not easily held, and also constrains effective use of solubility promoter to a certain extent.
Due to environmental requirement, paper mill sludge must process, and in prior art, is all confined to landfill, compost and burning to the treatment process of paper mill sludge, there are no other process or Land use systems.And the present inventor finds in research, test: gasification altogether after by paper mill sludge and coal Homogeneous phase mixing, coal ash can be improved in gasification, reduce coal ash fusion temperature, lime-ash is discharged in liquid form smoothly.After further study, its reason may be the basic cpd having high level in paper mill sludge, also unexpected discovery simultaneously, although the acidic cpd also containing high level in paper mill sludge, but it creates high ash melting point raw coal suitability widely on the contrary, better ash fusion point temperature regulating power: ash fusion point temperature can be reduced to 1380 DEG C from > 1450 DEG C by the addition as 6%, even ash fusion point temperature can be reduced to 1241 DEG C from > 1450 DEG C at the addition of 10%, and addition unrestriction: namely no matter how high addition is, all can not there are other unfavorable problems such as ash fusion point improves on the contrary.
For the concrete reason occurring aforementioned unforeseeable good result, there is not research conclusion at present, but can certainly relevant with the specific composition of the paper mill sludge that the present invention adopts (paper mill sludge of the present invention has high calcium, and the silicon of low levels, iron, aluminium, the more magnesium of low levels, and the special proportioning of a small amount of sodium, potassium and manganese), make the present invention thus.
The object of the invention is realized by following technical proposals:
A kind of fusing assistant reducing gasified pulverized coal slag ash fusion point temperature, it is characterized in that: described fusing assistant is paper mill sludge, described paper mill sludge contains organism, empty butt thermal value is 800 kilocalories/kg ~ 1000 kilocalorie/kg, basic oxide mass content more than 50%, its chemical composition and mass content thereof are: CaO40% ~ 56%, MgO3% ~ 12%, Al 2o 33% ~ 12%, Fe 2o 39% ~ 15%, SiO 214% ~ 20%, SO 3< 3%, TiO 2< 0.8%, and mass content is the alkalimetal oxide of less than 1% and a small amount of impurity.
As selection, chemical composition and mass content thereof consist of: CaO50% ~ 56%, MgO3% ~ 4%, Al 2o 39% ~ 11%, Fe 2o 310% ~ 15%, SiO 214% ~ 17%, SO 3< 3%, TiO 2< 0.8%, K 2o0.1% ~ 0.3%, Na 2o0.2% ~ 0.3%, MnO0.09% ~ 0.12% and a small amount of impurity.
Described impurity is generally the heavy metals such as P, Li, Pd, and total content is usually below 2.3%.
A kind of using method of aforementioned fusing assistant, it is characterized in that: when the texturing temperature less than 1450 DEG C of feed coal, the add-on of fusing assistant accounts for 6% ~ 15% of fusing assistant and feed coal gross weight, when the texturing temperature of feed coal is higher than 1450 DEG C, the add-on of fusing assistant accounts between fusing assistant and 15% ~ 30% of feed coal gross weight.
Beneficial effect of the present invention: paper mill sludge fusing assistant of the present invention be can with altogether gasification after coal Homogeneous phase mixing, coal ash can be improved in gasification, reduce coal ash fusion temperature, lime-ash is discharged in liquid form smoothly, make high ash melting point coal sample also go for the vapourizing furnace application of slag tap technology, widen the Suitability of Coals of slag tap technology vapourizing furnace.
Paper mill sludge fusing assistant of the present invention is also fuel while of being fusing assistant.In gasification, it can meet while existing slag tap gasification technology requires coal ash fusion temperature in the slag characteristic improving high-melting-point coal, can reach the object of economizing on coal.
Adopt paper mill sludge fusing assistant of the present invention, the method can effectively avoiding current vapourizing furnace to add Wingdale reduces coal ash fusion temperature, and easily interpolation too much causes the problem of stifled slag.Meanwhile, this solubility promoter adopts less consumption can reduce ash fusion point temperature significantly, and to addition unrestriction.
Paper mill sludge is that a large amount of mud produced in various paper product process are being manufactured in paper mill, and along with production and the rapid development of economy of China's paper industry, the generation of paper mill sludge also increases sharply.The treatment process of China to paper mill sludge has landfill, compost and burning.The mode disposed its process at present, mainly based on landfill, only has part to be fully utilized, and paper mill sludge is used as fusing assistant and opens that a paper mill sludge is turned waste into wealth, the new way of recycling.
Embodiment
Following non-limiting examples is for illustration of the present invention.
Reduce a fusing assistant for gasified pulverized coal slag ash fusion point temperature, described fusing assistant is paper mill sludge, and paper mill sludge can be hygrometric state, also can dry or drying and processing after product through spontaneous combustion.Described paper mill sludge contains organism, and empty butt thermal value is 800 kilocalories/kg ~ 1000 kilocalorie/kg, and basic oxide mass content more than 50%, its chemical composition and mass content thereof are: CaO40% ~ 56%, MgO3% ~ 12%, Al 2o 33% ~ 12%, Fe 2o 39% ~ 15%, SiO 214% ~ 20%, SO 3< 3%, TiO 2< 0.8%, and mass content is the alkalimetal oxide of less than 1% and a small amount of impurity.
For the paper mill sludge sample of Chongqing paper company, the technical analysis of described paper mill sludge fusing assistant and ultimate analysis are in table one, and composition analysis is in table two.
Specific implementation process: paper mill sludge sample and Shell vapourizing furnace high ash melting point coal sample, can be prepared according to GB/T474-2008 " preparation method of coal sample ", GB/T1574-2007 " coal ash analysis method " and GB/T219-2008 " measuring method of coal ash melting property " and measure.The coal ash meltbility temperature of coal ash sample is detected with intelligent ash melting tester, for ensureing to make the ash fusion point of the mixing ash sample of fusing assistant and feed coal lower than 1400 DEG C, if the texturing temperature of coal ash is lower than 1450 DEG C, then the addition of paper mill sludge fusing assistant accounts for 6% ~ 15% of fusing assistant and feed coal gross weight; If the texturing temperature of coal ash is higher than 1450 DEG C, then the addition of paper mill sludge fusing assistant accounts for 15% ~ 30% of fusing assistant and feed coal gross weight.Due to the difference of the characteristic such as composition of high ash melting point coal sample, the interpolation scope roughly of paper mill sludge fusing assistant can only be provided.
Embodiment 1 chooses the high ash melting point coal sample of Shanxi power plant, pulverized coal sample is prepared by above-mentioned standard method, coal ash texturing temperature 1420 DEG C is drawn with the analysis of intelligent ash melting tester, paper mill sludge fusing assistant powder is added in the high ash melting point coal dust sample of this power plant with 6% ratio, after mixing, prepares mixing ash sample.
Embodiment 2 chooses the high ash melting point coal sample of Sichuan power plant, pulverized coal sample is prepared by above-mentioned standard method, coal ash texturing temperature > 1450 DEG C is drawn with the analysis of intelligent ash melting tester, paper mill sludge fusing assistant powder is added in this power plant's high ash melting point coal dust sample with 15% ratio, after mixing, prepares mixing ash sample.
Embodiment 3 chooses the high ash melting point coal sample of Xinjiang company, pulverized coal sample is prepared by above-mentioned standard method, coal ash texturing temperature 1248 DEG C is drawn with the analysis of intelligent ash melting tester, paper mill sludge fusing assistant powder is added in the high ash melting point coal dust sample of the said firm with 10% ratio, after mixing, prepares mixing ash sample.
Embodiment 4 chooses the high ash melting point coal sample of Inner Mongol power plant, pulverized coal sample is prepared by above-mentioned standard method, coal ash texturing temperature > 1450 DEG C is drawn with the analysis of intelligent ash melting tester, paper mill sludge fusing assistant powder is added in the high ash melting point coal dust sample of this power plant with 15% ratio, after mixing, prepares mixing ash sample.
Embodiment 5 chooses the high ash melting point coal sample of Inner Mongol power plant, pulverized coal sample is prepared by above-mentioned standard method, show that coal ash texturing temperature is > 1450 DEG C with the analysis of intelligent ash melting tester, paper mill sludge fusing assistant powder is added in the high ash melting point coal dust sample of this power plant with 30% ratio, after mixing, prepares mixing ash sample.
Embodiment 6 chooses the high ash melting point coal sample of Anhui power plant, pulverized coal sample is prepared by above-mentioned standard method, show that coal ash texturing temperature is 1293 DEG C with the analysis of intelligent ash melting tester, paper mill sludge fusing assistant powder is added in the high ash melting point coal dust sample of this power plant with 10% ratio, after mixing, prepares mixing ash sample.
Embodiment 7 chooses the high ash melting point coal sample of Hebei power plant, pulverized coal sample is prepared by above-mentioned standard method, show that coal ash texturing temperature is 1402 DEG C with the analysis of intelligent ash melting tester, paper mill sludge fusing assistant powder is added in the high ash melting point coal dust sample of this power plant with 10% ratio, after mixing, prepares mixing ash sample.
Embodiment 8 chooses Henan power plant high ash melting point coal sample, pulverized coal sample is prepared by above-mentioned standard method, show that coal ash texturing temperature is 1450 DEG C with the analysis of intelligent ash melting tester, paper mill sludge fusing assistant powder is added in the high ash melting point coal dust sample of this power plant with 10% ratio, after mixing, prepares mixing ash sample.
The present invention in use according to the requirement of vapourizing furnace to coal ash melting property, can suitably regulate the addition of fusing assistant.
The experimental study that embodiment 9 paper mill sludge fusing assistant affects coal ash melting property.Specifically in table three, table four and table five.
The fusing assistant technical analysis of table one paper mill sludge and Elemental analysis data:
Table two paper mill sludge flux constituents is analyzed and grey melt temperature analytical data:
The grey chemical composition analytical data of table three coal sample:
Table four paper mill sludge fusing assistant is on the impact (wherein DT is texturing temperature, and ST is softening temperature, and HT is hemispherical temperature, and FT is yield temperature) of coal ash melting property:
Remarks: adding proportion is the ratio that the add-on of fusing assistant accounts for fusing assistant and feed coal gross weight.
Example effects of fluxing (being added to example with the coal sample of embodiment 2) when table five paper mill sludge fusing assistant heavy dose is added:
Sequence number Adding proportion Texturing temperature Softening temperature Hemispherical temperature Yield temperature
1 0.99% 1417 >1450℃ >1450℃ >1450℃
2 1.96% 1389 >1450℃ >1450℃ >1450℃
3 2.91% 1382 1431 1442 >1450℃
4 3.85% 1358 1416 1421 1430
5 4.76% 1361 1415 1418 1424
6 5.40% 1360 1396 1401 1408
7 6.54% 1374 1392 1397 1407
8 7.41% 1369 1400 1404 1406
9 8.26% 1361 1403 1409 1413
10 10% 1368 1405 1410 1416
11 11% 1376 1402 1410 1416
12 12% 1378 1408 1414 1422
13 13% 1354 1408 1414 1419
14 14% 1332 1381 1388 1397
15 15% 1292 1365 1386 1389
16 16% 1274 1345 1360 1371
17 17% 1277 1308 1314 1321
18 18% 1204 1273 1285 1299
19 19% 1233 1248 1258 1265
20 20% 1200 1238 1244 1249
21 21% 1220 1232 1237 1241
22 22% 1213 1232 1238 1243
23 23% 1219 1227 1231 1238
24 24% 1219 1225 1231 1238
25 25% 1213 1224 1230 1235
26 26% 1194 1221 1229 1237
27 27% 1209 1226 1230 1236
28 28% 1215 1223 1230 1239
29 29% 1187 1222 1227 1234
30 30% 1218 1228 1235 1255
31 31% 1212 1236 1244 1250
32 32% 1236 1245 1253 1265
33 33% 1232 1249 1258 1269
34 34% 1239 1258 1278 1286
35 35% 1227 1263 1279 1292
36 36% 1252 1278 1286 1295
37 37% 1238 1294 1312 1322
38 38% 1262 1305 1326 1334
39 39% 1263 1318 1329 1336
40 40% 1280 1329 1340 1349
41 41% 1303 1335 1355 1362
42 42% 1313 1349 1354 1358
43 43% 1274 1346 1360 1371
44 44% 1332 1350 1360 1367
45 45% 1296 1356 1362 1368
46 46% 1280 1358 1364 1370
47 47% 1290 1358 1363 1368
48 48% 1300 1357 1366 1371
49 49% 1332 1359 1365 1375
50 50% 1288 1360 1366 1371
51 55% 1321 1368 1377 1382
52 60% 1352 1364 1370 1375
53 65% 1324 1344 1358 1380
54 70% 1314 1331 1338 1342
55 75% 1333 1349 1354 1360
56 80% 1350 1372 1373 1385
57 85% 1371 1375 1382 1392
58 90% 1280 1376 1386 1392
59 95% 1294 1372 1386 1391
The patent of invention that comparative example 1CN1970698 discloses " a kind of fusing assistant reducing coal ash fusion temperature and preparation method thereof ", fusing assistant described in it is that described fusing assistant has following component (% by weight): CaCO for reducing producing the ash fusion point of lime-ash in coal gasification course and the additive added in coal 382% ~ 93%; Fe 2o 32% ~ 16%, surplus is MgCO 3.This solubility promoter addition accounts for 25% ~ 32% of solubility promoter and feed coal gross weight, as follows to the ash fusion point test-results of Huainan coal:
From previous embodiment and comparative example: fusing assistant of the present invention is mixed in high ash melting point coal sample, can effectively reduce coal ash fusion temperature temperature, make high ash melting point coal sample also go for the vapourizing furnace application of slag tap technology.There are three distinguishing features simultaneously:
1, suitability is extensive, all has good reduction ash fusion point temperature action to high-ash-fusion coal widely;
2, consumption is few, and ash fusion point temperature reduction amplitude is large;
3, do not have usage quantity restricted, up to equally having good reduction ash fusion point temperature action under 50% and above addition in table five.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.

Claims (3)

1. one kind is reduced the fusing assistant of gasified pulverized coal slag ash fusion point temperature, it is characterized in that: described fusing assistant is paper mill sludge, described paper mill sludge contains organism, empty butt thermal value is 800 kilocalories/kg ~ 1000 kilocalorie/kg, basic oxide mass content more than 50%, its chemical composition and mass content thereof are: CaO40% ~ 56%, MgO3% ~ 12%, Al 2o 33% ~ 12%, Fe 2o 39% ~ 15%, SiO 214% ~ 20%, SO 3< 3%, TiO 2< 0.8%, and mass content is less than 1% alkalimetal oxide and a small amount of impurity.
2. the fusing assistant reducing gasified pulverized coal slag ash fusion point temperature as claimed in claim 1, is characterized in that chemical composition and mass content thereof consist of: CaO50% ~ 56%, MgO3% ~ 4%, Al 2o 39% ~ 11%, Fe 2o 310% ~ 15%, SiO 214% ~ 17%, SO 3< 3%, TiO 2< 0.8%, K 2o0.1% ~ 0.3%, Na 2o0.2% ~ 0.3%, MnO0.09% ~ 0.12% and a small amount of impurity.
3. the using method of the fusing assistant described in a claim 1 or 2, it is characterized in that: when the texturing temperature less than 1450 DEG C of feed coal, the add-on of fusing assistant accounts for 6% ~ 15% of fusing assistant and feed coal gross weight, when the texturing temperature of feed coal is higher than 1450 DEG C, the add-on of fusing assistant accounts between fusing assistant and 15% ~ 30% of feed coal gross weight.
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