CN103429706A - 沥青分离组合物和工艺过程 - Google Patents

沥青分离组合物和工艺过程 Download PDF

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CN103429706A
CN103429706A CN2010800477044A CN201080047704A CN103429706A CN 103429706 A CN103429706 A CN 103429706A CN 2010800477044 A CN2010800477044 A CN 2010800477044A CN 201080047704 A CN201080047704 A CN 201080047704A CN 103429706 A CN103429706 A CN 103429706A
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technique
sand
separated portion
pitch
mud
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罗伯特C·叶基
维托J·阿尔塔维拉
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VARY Petrochem LLC
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VARY Petrochem LLC
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Priority claimed from US12/556,878 external-priority patent/US7758746B2/en
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/04Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction

Abstract

用分离组分分离回收沥青混合物中的沥青回收工艺,主要包括以下过程:a.将沥青混合物和分离组分混合,得到泥浆;b.泥浆在高速高剪切混合器中充分搅拌,得到混合均匀的泥浆;c.混合后的泥浆至少分为三层,包括:一沥青层,一分离组分层,一固体层;d.脱离沥青层,其中沥青层含粘土和砂粒的重量分数小于2%。

Description

沥青分离组合物和工艺过程
背景技术
油砂亦称“焦油砂”、“沥青砂”,实质上是一种由沥青(焦油)、砂和水组成的混合物。沥青是一种具有高密度、高粘度的原油,且硫的含量相当高。如果采用是适当的工艺从油砂中分离沥青,提炼出的沥青可以用来合成原油,这种原油可以用作生产液体汽油,燃料油以及石化产品的原料。世界上油砂资源的分布非常广泛,特别集中在加拿大阿尔伯塔省的阿沙巴斯克油砂区、美国犹他油砂区、南美洲的委内瑞拉油砂区以及非洲的尼日利亚油砂区。世界上已查明的石油主要存在于油砂。
从油砂中提炼沥青很难做到既高效又环保。目前的技术只能将油砂中85-92%的沥青分离出来,同时,提炼沥青过程中会产生乳状液或者残渣等废物,而此类废物的“破坏”处理需要使用对环境有害的有机溶剂如石脑油等物质,而且,滞留在砂中未被提炼出的沥青(以及其他物质,例如粘土)等成分会导致污泥的形成,也就是形成声名狼藉的“尾矿”。这些尾矿由残存的沥青、砂、水等污染物组成。目前对这些尾矿的处理是将其引入巨大的尾矿池,经历一段的年月,尾矿中的砂和其他污染物被逐渐的沉积和分层。
发明内容
本发明推广和阐述一种高效且环保的可将沥青从油砂中提炼出来的化学组合物和方法。该方法也可以将残留的沥青从尾矿或其他含有沥青的物料中分离出来。
本发明采用的分离组合物的主要方案之一是分离成分中包含了一种水溶助长剂和一种具有絮凝特性的分散剂。分离组分的pH值大于7.5。本发明的另一个方案是添加了一种润湿剂的分离成分,润湿剂的含量约占分离成分的0.001%-2.5%;其组成中也包含了一种水溶助长剂和一种具有絮凝特性的分散剂,分离成分的pH值大于7.5。
本发明方案之一,分离成分的组成包括含量约0.1%-4.0%的水溶助长剂以及含量约0.25%-4.5%的具有絮凝特性的分散剂。根据本发明实施例,另一个分离组合物的方案是含有约0.001%-2.5%的润湿剂;0.1%-4.0%的水溶助长剂;约0.25%-4.5%的具有絮凝特性的分散剂。
本发明实施例的主要内容还包括可以将沥青从油砂或者尾矿中分离的组合物方案。该组成包含了约0.1%-4.0%的芳香族磷酸酯,其化学式如下:
Figure BPA00001545693600021
式中R1是C1-C5线性或支化烷基;n=1-8;含有约为0.001%-4.5%的焦磷酸钠;含有约为0.001%-4.5%的焦磷酸钾;含有约为2%-9.5%的氢氧化钠;含有约为1.7%-8.6%的磷酸。分离成分的pH值约为7.0-8.5。根据本发明实施例,另一个将沥青从油砂或者尾矿中分离的组合物方案包含了0.001%-2.5%的2,5,8,11-四甲基-6-十二炔-5,8-二醇异氧化合物;约0.1%-4.0%的芳香族磷酸酯,其化学式如下:
Figure BPA00001545693600022
式中R1是C1-C5线性或支化烷基;n=1-8;含有约为0.001%-4.5%的焦磷酸钠;含有约为0.001%-4.5%的焦磷酸钾;含有约为2%-9.5%的氢氧化钠;含有约为1.7%-8.6%的磷酸,分离成分的pH值约为7.0-8.5。
具体实施方式
这里用的术语“大约(about)”意为“近似(approximately)”,且在任何情况下,表示数据误差偏离10%。
这里用的术语“essentially free”意为含量上少于0.1%。
发明实施例中提供的组合物为分离成分的组成,包含了一种水溶助长剂和一种具有絮凝特性的分散剂,分离组成物的pH值大于7.5。
发明实施例中提供的组合物还包含了一种润湿剂,润湿剂的含量占分离成分的比例从约0.001%到约2.5%不等。在其他方案中,润湿剂的含量占分离成分的比例从约0.001%到约1%,约0.01%到约2.5%,约0.01%到约1%,或者约0.1%到约0.5%。适合的润湿剂可能包括如下所述产品:例如,DYNOLTM607表明活性剂(Air Products and Chemicals,Inc),
Figure BPA00001545693600031
420(Air Productsand  Chemicals,Inc),
Figure BPA00001545693600032
440(Air Products and Chemicals,Inc),
Figure BPA00001545693600033
465(Air Products and Chemicals,Inc),
Figure BPA00001545693600034
485(AirProducts and Chemicals,Inc),DYNOLTM 604表明活性剂(Air Products andChemicals,Inc),
Figure BPA00001545693600035
91-2.5(Tomah Products,Inc),
Figure BPA00001545693600036
91-6(Tomah Products,Inc),
Figure BPA00001545693600037
91-8(Tomah Products,Inc),
Figure BPA00001545693600038
1-3(Tomah Products,Inc),1-5(Tomah Products,Inc),
Figure BPA000015456936000310
1-7(Tomah Products,Inc),
Figure BPA000015456936000311
1-73B(Tomah Products,Inc),
Figure BPA000015456936000312
1-9(Tomah Products,Inc),
Figure BPA000015456936000313
23-1(Tomah Products,Inc),23-3(Tomah Products,Inc),23-5(Tomah Products,Inc),23-6.5(Tomah Products,Inc),
Figure BPA000015456936000317
25-3(TomahProducts,Inc),
Figure BPA000015456936000318
25-7(Tomah Products,Inc),
Figure BPA000015456936000319
25-9(Tomah Products,Inc),
Figure BPA000015456936000320
25-12(Tomah Products,Inc),
Figure BPA000015456936000321
45-7(Tomah Products,Inc),45-13(Tomah Products,Inc),TRITONTMX-207表明活性剂(Dow Chemical Company),TRITONTMCA表明活性剂(Dow Chemical Company),NOVECTM荧光表明活性剂FC-4434(3MCompany),POLYFOXTMAT-1118B(Omnova Solutions,Inc),
Figure BPA000015456936000323
210(Dupont),
Figure BPA000015456936000324
225(Dupont),321(Dupont),8740(Dupont),
Figure BPA000015456936000327
8834L(Dupont),
Figure BPA000015456936000328
8857A(Dupont),
Figure BPA000015456936000329
8952(Dupont),
Figure BPA000015456936000330
9027(Dupont),
Figure BPA000015456936000331
9338(Dupont),9360(Dupont),9361(Dupont),
Figure BPA000015456936000334
9582(Dupont),9671(Dupont),
Figure BPA000015456936000336
FS-300(Dupont),
Figure BPA000015456936000337
FS-500(Dupont),
Figure BPA000015456936000338
FS-610(Dupont),
Figure BPA000015456936000339
1033D(Dupont),
Figure BPA000015456936000340
FSJ(Dupont),
Figure BPA000015456936000341
FSA(DuPont),
Figure BPA000015456936000342
FSN-100(Dupont),OP 30-70%(BASF),
Figure BPA000015456936000344
A 12 N(BASF),
Figure BPA000015456936000345
A 3 N(BASF),
Figure BPA000015456936000346
A 65 N(BASF),
Figure BPA000015456936000347
A 9 N(BASF),
Figure BPA000015456936000348
AO 3(BASF),
Figure BPA000015456936000349
AO 4(BASF),
Figure BPA000015456936000350
AO 8(BASF),
Figure BPA000015456936000351
AT 25(BASF),
Figure BPA000015456936000352
AT 55金属颗粒表面活性剂(BASF),CF 10 90表面活性剂(BASF),
Figure BPA000015456936000354
DNP 10(BASF),
Figure BPA000015456936000355
NP 4(BASF),
Figure BPA000015456936000356
NP 10(BASF),
Figure BPA00001545693600041
NP-100片剂(BASF),NP-6(BASF),
Figure BPA00001545693600043
NP-70-70% 10(BASF),
Figure BPA00001545693600044
NP-5O(BASF),
Figure BPA00001545693600045
NP 9(BASF),
Figure BPA00001545693600046
ON 40表面活性剂(BASF),
Figure BPA00001545693600047
ON 60(BASF),OP-10(BASF),
Figure BPA00001545693600049
TDA 10表面活性剂(BASF),
Figure BPA000015456936000410
TDA 3表面活性剂(BASF),
Figure BPA000015456936000411
TDA 6表面活性剂(BASF),
Figure BPA000015456936000412
TDA9表面活性剂(BASF),
Figure BPA000015456936000413
XL 69(BASF),XL 100(BASF),XL 140(BASF),
Figure BPA000015456936000416
XL 40(BASF),XL 50(BASF),XL 60(BASF),
Figure BPA000015456936000419
XL 70(BASF),
Figure BPA000015456936000420
XL 79(BASF),
Figure BPA000015456936000421
XL 80(BASF),XL 89(BASF),XL 90(BASF),
Figure BPA000015456936000424
XL 99(BASF),
Figure BPA000015456936000425
XP 100(BASF),
Figure BPA000015456936000426
XP 140(BASF),
Figure BPA000015456936000427
XP 30(BASF),
Figure BPA000015456936000428
XP 40(BASF),
Figure BPA000015456936000429
XP 50(BASF),XP 60(BASF),
Figure BPA000015456936000431
XP 69(BASF),
Figure BPA000015456936000432
XP 70(BASF),
Figure BPA000015456936000433
XP 79(BASF),XP 80(BASF),
Figure BPA000015456936000435
XP 89(BASF),
Figure BPA000015456936000436
XP 90(BASF),
Figure BPA000015456936000437
XP 99(BASF),
Figure BPA000015456936000438
16表面活性剂(BASF),
Figure BPA000015456936000439
CSA 20聚酯纤维(BASF),
Figure BPA000015456936000440
LA 12表面活性剂(BASF),
Figure BPA000015456936000441
LA 4表面活性剂(BASF),
Figure BPA000015456936000442
LA 10表面活性剂(BASF),
Figure BPA000015456936000443
LF 125A表面活性剂(BASF),
Figure BPA000015456936000444
1651表面活性剂(BASF),
Figure BPA000015456936000445
LDA月桂基胺氧化物表面活性剂(BASF),AO8A表面活性剂(BASF),
Figure BPA000015456936000447
B-26表面活性剂(BASF),
Figure BPA000015456936000448
B25-5表面活性剂(BASF),
Figure BPA000015456936000449
D25表面活性剂(BASF),LF 1200表面活性剂(BASF),
Figure BPA000015456936000451
LF 2210表面活性剂(BASF),
Figure BPA000015456936000452
LF 4030表面活性剂(BASF),
Figure BPA000015456936000453
LF 7000表面活性剂(BASF),
Figure BPA000015456936000454
RA-20表面活性剂(BASF),
Figure BPA000015456936000455
RA 30表面活性剂(BASF),RA 40表面活性剂(BASF),
Figure BPA000015456936000457
RCS 43表面活性剂(BASF),
Figure BPA000015456936000458
RCS 48表面活性剂(BASF),
Figure BPA000015456936000459
S205LF表面活性剂(BASF),
Figure BPA000015456936000460
S305LF表面活性剂(BASF),
Figure BPA000015456936000461
S505LF表面活性剂(BASF),
Figure BPA000015456936000462
SL 62表面活性剂(BASF),
Figure BPA000015456936000463
SL 92表面活性剂(BASF),SL-22表面活性剂(BASF),
Figure BPA000015456936000465
SL-42表面活性剂(BASF),
Figure BPA00001545693600051
SLF 37表面活性剂(BASF),
Figure BPA00001545693600052
SLF-18表面活性剂(BASF),
Figure BPA00001545693600053
SLF-18B-45表面活性剂(BASF),L1220表面活性剂(BASF),
Figure BPA00001545693600055
10R5表面活性剂(BASF),
Figure BPA00001545693600056
17R2表面活性剂(BASF),
Figure BPA00001545693600057
17R4表面活性剂(BASF),25R2表面活性剂(BASF),
Figure BPA00001545693600059
25R4表面活性剂(BASF),
Figure BPA000015456936000510
31R1表面活性剂(BASF),
Figure BPA000015456936000511
F108整体铸造表面活性剂(BASF),
Figure BPA000015456936000512
F108NF整体铸造表面活性剂(BASF),
Figure BPA000015456936000513
F108 NF颗粒表面活性剂(BASF),
Figure BPA000015456936000514
F108片剂表面活性剂(BASF),
Figure BPA000015456936000515
F127整体铸造表面活性剂(BASF),
Figure BPA000015456936000516
F127 NF颗粒表面活性剂(BASF),
Figure BPA000015456936000517
F127NF 500BHT整体铸造表面活性剂(BASF),
Figure BPA000015456936000518
F38整体铸造表面活性剂(BASF),
Figure BPA000015456936000519
片剂表面活性剂(BASF),
Figure BPA000015456936000520
F68 LF片剂表面活性剂(BASF),
Figure BPA000015456936000521
F68整体铸造表面活性剂(BASF),
Figure BPA000015456936000522
F77整体铸造表面活性剂(BASF),
Figure BPA000015456936000523
F-77微片剂表面活性剂(BASF),
Figure BPA000015456936000524
F87整体铸造表面活性剂(BASF),
Figure BPA000015456936000525
F88整体铸造表面活性剂(BASF),
Figure BPA000015456936000526
F98整体铸造表面活性剂(BASF),
Figure BPA000015456936000527
L10表面活性剂(BASF),
Figure BPA000015456936000528
L101表面活性剂(BASF),
Figure BPA000015456936000529
L121表面活性剂(BASF),
Figure BPA000015456936000530
L131表面活性剂(BASF),L92表面活性剂(BASF),
Figure BPA000015456936000532
N-3表面活性剂(BASF),
Figure BPA000015456936000533
P103表面活性剂(BASF),
Figure BPA000015456936000534
P105表面活性剂(BASF),
Figure BPA000015456936000535
P123表面活性剂(BASF),
Figure BPA000015456936000536
P65表面活性剂(BASF),
Figure BPA000015456936000537
P84表面活性剂(BASF),
Figure BPA000015456936000538
P85表面活性剂(BASF),
Figure BPA000015456936000539
1107微片剂表面活性剂(BASF),
Figure BPA000015456936000540
1301表面活性剂(BASF),
Figure BPA000015456936000541
1304表面活性剂(BASF),
Figure BPA000015456936000542
1307表面活性剂(BASF),
Figure BPA000015456936000543
1307表面活性剂微片剂(BASF),
Figure BPA000015456936000544
150R1表面活性剂(BASF),
Figure BPA000015456936000545
304表面活性剂(BASF),701表面活性剂(BASF),901整体铸造表面活性剂(BASF),
Figure BPA000015456936000548
904表面活性剂(BASF),
Figure BPA000015456936000549
908表面活性剂(BASF),
Figure BPA000015456936000550
908片剂表面活性剂(BASF),这些产品中的一种或多种混合物可以用作分离组分中的润湿剂。发明实施例某一特例中的润湿剂可能包含一种或几种乙氧基炔醇化合物,例如,2,5,8,11-四甲基-6-十二炔-5,8-二醇异氧化合物。
发明的另一个方案的组分中可不包含润湿剂。组分中如果不包含润湿剂会增加组分的表面张力。降低表面张力可以促使组分形成乳状结构,而将组分用于油砂时,乳状结构会阻碍组分中的固体成分絮凝而脱离组分。而且降低表面张力可以进一步阻碍体系中机械能的传递。
适当水溶助长剂包含以下示例产品中的一种或几种混合物。例如:
Figure BPA00001545693600061
H-66(Dow Chemical Company),
Figure BPA00001545693600062
H-55(Dow ChemicalCompany),
Figure BPA00001545693600063
QS-44(Dow Chemical Company),
Figure BPA00001545693600064
XQS-20(DowChemical Company),
Figure BPA00001545693600065
X-15(Union Carbide Corporation),
Figure BPA00001545693600066
X-15(Union Carbide Corporation),
Figure BPA00001545693600067
X-35(Union CarbideCorporation),X-45(Union Carbide Corporation),X-114(Union Carbide Corporation),
Figure BPA000015456936000610
X-100(Union CarbideCorporation),
Figure BPA000015456936000611
X-165(70%)活性物(Union  CarbideCorporation),
Figure BPA000015456936000612
X-305(70%)活性物(Union CarbideCorporation),X-405(70%)活性物(Union CarbideCorporation),
Figure BPA000015456936000614
BG非离子表明活性剂(Union CarbideCorporation),
Figure BPA000015456936000615
MinForm 1X(Dow Chemical Company),
Figure BPA000015456936000616
L-61(Dow Chemical Company),L-64(Dow Chemical Company),
Figure BPA000015456936000618
L-81(Dow Chemical Company),L-101(DowChemical Company),NP-4(Dow Chemical Company),
Figure BPA000015456936000621
NP-6(Dow Chemical Company),
Figure BPA000015456936000622
NP-7(Dow ChemicalCompany),
Figure BPA000015456936000623
NP-8(Dow Chemical Company),
Figure BPA000015456936000624
NP-9(Dow Chemical Company),NP-11(Dow ChemicalCompany),
Figure BPA000015456936000626
NP-12(Dow Chemical Company),
Figure BPA000015456936000627
NP-13(Dow Chemical Company),
Figure BPA000015456936000628
NP-15(Dow ChemicalCompany),
Figure BPA000015456936000629
NP-30(Dow Chemical Company),
Figure BPA000015456936000630
NP-40(Dow Chemical Company),
Figure BPA000015456936000631
420(Air Products and Chemicals,Inc),
Figure BPA000015456936000632
440(Air Products and Chemicals,Inc),
Figure BPA000015456936000633
465(AirProducts and Chemicals,Inc),
Figure BPA000015456936000634
485(Air Products and Chemicals,Inc),
Figure BPA000015456936000635
58酯(BASF),
Figure BPA000015456936000636
60 A表面活性剂(BASF),
Figure BPA000015456936000637
66H酯(BASF),
Figure BPA000015456936000638
8135酯(BASF),M-60酯(BASF),6660 K助水溶剂磷酸酯盐(Burlington Chemical),Burofac7580芳香族磷酸酯(Burlington Chemical),以及Burofac 9125(BurlingtonChemical)。
发明实施例某一特例中的水溶助长剂包含一种或几种芳香族磷酸酯。例如某种芳香族磷酸酯化学式如下所示:
Figure BPA00001545693600071
式中R1是C1-C5线性或支化烷基;n=1-8。
适当的分散剂需具备絮凝特性,一般包含一种或几种以下示例化合物的混合物。例如,酸式焦磷酸钠,焦磷酸四钾,磷酸二氢钠(H6NaO6P),磷酸二氢铵((NH4)PO4),酸式磷酸钠,磷酸三钠,三聚磷酸钠,三偏磷酸钠,磷酸钠月桂,磷酸钠,三磷酸五钾,三磷酸钾,三聚磷酸四硼酸钾,磷酸二氢钾,磷酸一氢钾,磷酸一钾,磷酸三钾等。发明实施例某一特例中的具备絮凝特性分散剂可以包含一种或几种焦磷酸盐。例如,酸式焦磷酸钠和焦磷酸四钾。
在某些特例中,水溶助长剂的含量约为分离组分的0.1%-4.0%。在其他的特例中,水溶助长剂的含量分别约为分离组分的0.1%-2%,0.5%-4.0%,0.5%-2%,1%-2%或者1%-4%。具备絮凝特性的分散剂的含量约为分离组分的0.25%-4.5%。另外一些特例中具备絮凝特性的分散剂的含量分别约为分离组分的0.25%-2.5%,0.25%-1%,1%-4.5%,1%-3%或者1%-2.5%。
发明实施例中的分离组分通常还含有一种强碱。例如,碱金属和稀土的氢氧混合物:氢氧化钠,氢氧化钾,氢氧化钡,氢氧化铯,氢氧化锶,氢氧化钙,氢氧化锂,氢氧化铷,氢化钠,二异丙基氨锂和氨基钠。此处说的强碱是指化合物的pH值约为13。分离组分中“强碱”的含量约为2%-9.5%。其他特例中强碱的含量分别约为分离组分的2%-7%,2%-5%,4%-7%,或者4%-5%。
发明实施例中的分离组分通常还含有一种重酸。例如,磷酸,硝酸,硫酸,氢溴酸,高氯酸,氟乙酸,魔力酸(FSO3HSbF5),碳硼烷酸[H(CHB11Cl11)],三氟乙酸,乙酸以及乙酰水杨酸。此处说的“重”酸是通常指酸比重约大于1.5。而在某些特例中倾向选用比重约大于1.65的重酸。分离组分中重酸的含量约为1.7%-8.6%。其他特例中强碱的含量分别约为分离组分的2%-7%,2%-5%,4%-7%,或者4%-5%。
发明实施例中的分离组分的pH值通常大于7.5。分离组分的pH值也可以约为7.0到8.5之间。分离组分的pH值也可以约为7.4-8.5或者7.4-7.8。分离组分的pH值还可以约为7.6-7.8。
发明实施例中的组分基本上不含有机溶剂。此处的“有机溶剂”是指有机化合物以及含碳元素的化合物,例如:石脑油,笨以及其他碳氢化合物的溶剂。
除了分离组分,组成中也包含了含有碳氢化合物的原料,例如油砂,尾矿,污泥以及类似成分(如含有沥青的成分)。分离组分与含有碳氢化合物的原料的比例约为2∶3到1000∶1,2∶3到500∶1,2∶3到100∶1,2∶3到10∶1,2∶3到3∶2,2∶3到3∶1或者1∶1。
发明实施例中还给出了一种分离组合物,其水溶助长剂的含量分别约为0.1%-4.0%,0.1%-2%,0.5%-4.0%,0.5%-2%,1%-2%或者1%-4.0%。具备絮凝特性的分散剂的含量分别约为0.25%-4.5%,0.25%-2.5%,0.25%-1%,1%-4.5%,1%-3%或者1%-2.5%。分离组分的pH值约大于7.5;也可以约为7.0-8.5。7.4-8.5,7.4-7.8或者7.6-7.8。水溶助长剂可以是:例如,
Figure BPA00001545693600081
66H芳香族磷酸酯。具备絮凝特性的分散剂可以是:例如,酸式焦磷酸钠和焦磷酸四钾中的一种或两种。
发明实施例中的分离组分中的强碱可以选择例如,氢氧化钠。强碱的含量约为分离组分的2%-9.5%,2%-7%,2%-5%,4%-7%,或者4%-5%。发明实施例中的分离组分中的重酸可以选择例如,磷酸。而重酸的含量约为分离组分的1.7%-8.6%。2%-7%,2%-5%,4%-7%,或者4%-5%。分离组分基本上或者完全不含有机溶剂。
发明实施例中提供了一种可以从油砂或尾矿中分离出沥青的分离组合物。组分中芳香族磷酸酯的含量约为:0.1%-4.0%,0.1%-2%,0.5%-4.0%,0.5%-2%,1%-2%或者1%-4.0%。芳香族磷酸酯的化学式如下所示:
Figure BPA00001545693600082
式中R1是C1-C5线性或支化烷基;n=1-8;其焦磷酸钠的含量约为0%-4.5%,0.25%-4.5%,0.25%-2.5%,0.25%-1%,1%-4.5%,1%-3%或者1%-2.5%;其焦磷酸四钾的含量约为0%-4.5%,0.25%-4.5%,0.25%-2.5%,0.25%-1%,1%-4.5%,1%-3%或者1%-2.5%;其氢氧化钠的含量约为2%-9.5%,2%-7%,2%-5%,4%-7%或者4%-5%;其磷酸的含量约为1.7%-8.6%,2%-7%,2%-5%,4%-7%或者4%-5%。分离组分的pH值可以约为7.0-8.5,7.4-8.5,7.4-7.8或者7.6-7.8。分离组分中基本上不含有机溶剂。
发明实施例中提供了一种可以从油砂中分离出沥青的方法。方法中首先将含有水溶助长剂和絮凝性分散剂的分离组分与含有沥青和砂土的油砂混合,然后将分离组分与油砂一起加热、振荡,将沥青和砂土产品分离。分离组分的pH值应约大于7.5;可以约为7.0-8.5,7.4-8.5,7.4-7.8或者7.6-7.8。
发明实施例示例中分离组分可以含有含量约为0.1%-4.0%水溶助长剂以及含量约为0.25%-4.5%的絮凝性分散剂。
发明实施例的示例还阐明分离组分可以含有含量约为0.1%-4.0%芳香族磷酸酯,其化学是为;
Figure BPA00001545693600091
式中R1是C1-C5线性或支化烷基;n=1-8;其焦磷酸钠的含量约为0%-4.5%;焦磷酸四钾的含量约为0%-4.5%;氢氧化钠的含量约为2%-9.5%;磷酸的含量约为1.7%-8.6%。
发明实施例示例中给出了分离过程中的具体条件。分离组分与油砂的加热温度需大于25℃(77°F);加热温度范围可以控制在约为32℃(90°F)-72℃(162°F)或是54℃(129°F)-60℃(140°F)。任何可将温度控制在工作范围内的常规的加热热源均可被采用。同样,任何可以将分离组分与油砂(或者其他含有沥青或者含有碳氢化合物或者其他原料)通过充分振荡破碎的常规仪器均可被选用,例如,高剪切混合机,高速研磨器,高速分散器,流化床,超声波混合仪,以及其他所有类似的可以提供在要求工作范围内充分振荡的常规仪器。此处,充分的振荡定义为经过振荡(或者混合)后的混合泥浆中的沥青颗粒被高剪切性或者高分散性的分离液所包溶,振荡时间不超过5分钟,泥浆温度大约为140°F,含有沥青的组分将有99%沥青会从泥浆中分离出来,并且浮在体系的上层形成沥青层,而沥青层中的固体物(例如砂土和粘土)的含量不超过2%。此处的高剪切定义为将混合物中所有颗粒物(包括颗粒度为5-200nm的颗粒)充分的机械分散,从而使得混合物中所有颗粒相互分离。这样的混合物呈单片状,尽管包含不同的成分但整体均匀,没有条纹状,水珠状;且易于区分像油砂这样含有碳氢化合物的凝聚团。
发明实施例中阐明,分离组分与油砂的比例约为2∶3到3∶2。发明实施例中也指出了分离组分与油砂的比例可以约为2∶3到1000∶1,2∶3到500∶1,2∶3到100∶1,2∶3到10∶1,2∶3到3∶2,2∶3到3∶1或者1∶1。
提炼出的沥青基本上不呈乳状。发明实施例示例的过程中没有添加任何有机溶剂。
在某些情况下,可以再次利用第二份等份的分离组分将分离提炼出来的沥青重复分离。这种情况下,示例方法中进一步将已经分离提炼出的沥青与另一份等份的分离组分混合,然后将新的分离组分与沥青一起加热、振荡,进一步提炼沥青。这种循环“冲洗”可以重复多次直到沥青中基本不再含有砂土和其他物质。
发明实施例中也指出在某些情况下分离组分可以重复使用。这种情况下,示例中的方法还包含了分离组分的回收,然后将回收后的分离组分与另一份等份的含有沥青和砂石的油砂混合,然后将回收的分离组分与新的待分离的油砂加热、振荡,提炼出沥青和砂石等产品。这种回收或者循环使用的分离组分也可以用来进一步对已提炼出来的沥青进行二次分离。
发明实施例中还给出了含有尾矿时的处理方案,包括了如何将尾矿中沉积的沥青分离出来以及如何将不含沥青的砂土重新沉积。方法中指出,可先将含有水溶助长剂和絮凝性分散剂的分离组分与含有沥青和砂土的尾矿混合,然后将分离组分与尾矿一起加热、振荡,将沥青和砂土产品分离。分离组分的pH值应约大于7.5;可以约为7.0-8.5;7.4-8.5;7.4-7.8或者7.6-7.8。
发明实施例示例处理尾矿的方法中分离组分可以含有含量约为0.1%-4.0%水溶助长剂以及含量约为0.25%-4.5%的絮凝性分散剂。发明实施例中还给出了分离组合物中的水溶助长剂的含量可以分别约为0.1%-2%,0.5%-4.0%,0.5%-2%,1%-2%或者1%-4.0%;具备絮凝特性的分散剂的含量可以分别约为0.25%-2.5%,0.25%-1%,1%-4.5%,1%-3%或者1%-2.5%。
发明实施例的示例还阐明处理尾矿的方法中分离组分可以含有含量约为0.1%-4.0%芳香族磷酸酯,其化学是为;
Figure BPA00001545693600111
式中R1是C1-C5线性或支化烷基;n=1-8;其焦磷酸钠的含量约为0%-4.5%;焦磷酸四钾的含量约为0%-4.5%;氢氧化钠的含量约为2%-9.5%;磷酸的含量约为1.7%-8.6%。方法中也给出了其他方案。芳香族磷酸酯的含量可以约为:0.1%-2%,0.5%-4.0%,0.5%-2%,1%-2%或者1%-4.0%,芳香族磷酸酯的化学式为:
Figure BPA00001545693600112
式中R1是C1-C5线性或支化烷基;n=1-8;其焦磷酸钠的含量约为0.25%-4.5%,0.25%-2.5%,0.25%-1%,1%-4.5%,1%-3%或者1%-2.5%;焦磷酸四钾的含量约为0.25%-4.5%,0.25%-2.5%,0.25%-1%,1%-4.5%,1%-3%或者1%-2.5%;氢氧化钠的含量约为2%-7%,2%-5%,4%-7%或者4%-5%;磷酸的含量约为2%-7%,2%-5%,4%-7%或者4%-5%。
发明实施例示例中给出了含有尾矿时分离过程中的具体条件。分离组分与油砂的加热温度需大于25℃(77°F);加热温度范围可以控制在约为32℃(90°F)-72℃(162°F)或是54℃(129°F)-60℃(140°F)。任何可将温度控制在工作范围内的常规的加热热源均可被采用。同样,任何可以将分离组分与尾矿通过充分振荡破碎的常规仪器均可被选用,例如,高剪切混合机,高速研磨器,高速分散器,流化床,超声波混合仪,以及其他所有类似的可以提供在要求工作范围内充分振荡的常规仪器。
发明实施例中阐明,分离组分与尾矿的比例约为2∶3到3∶2。发明实施例中也给出了分离组分与尾矿的比例还可以约为2∶3到1000∶1,2∶3到500∶1,2∶3到100∶1,2∶3到10∶1,2∶3到3∶2,2∶3到3∶1或者1∶1。
提炼出的沥青基本上不呈乳状。发明实施例示例的过程中没有添加任何有机溶剂。
发明实施例给出的沥青的提炼过程可以将含有沥青原料(例如,油砂,污泥,尾矿等等)中99%的沥青分离出来。示例中沥青回收过程中没有使用任何有机溶剂从而消除了由于使用此类溶剂而给环境带来的危害。发明实施例还指出使用所述分离组分可以高效的将沥青从含有沥青的原料中提炼出来(例如,97%,98%,99%,99.5%)。
沥青回收过程的示例中可以选择性使用将含有沥青的原料进行磨碎的方法。例如,犹他地区的油砂对于磨碎的方法很有效。磨碎过程包括将含有沥青的原料碎成颗粒或是打散,使得形成的颗粒易于在沥青回收过程中进一步的机械处理。在某些情况下,经过磨碎的颗粒成分的大小可以约为未经过磨碎过程的平均颗粒大小的额“1/16”到“1/4”。研磨过程可以由熟练掌握机械研磨方法以及研磨机器(例如,磨床,碎料机等等)的工人操作。是否需要磨碎过程一般是根据含有沥青的原料颗粒大小来判断。而含有沥青的原料颗粒的大小由原料(例如油砂)的来源,原料的沉积时间及沉积的条件来决定(即由温度的高低以及受压程度等条件来决定)。
研磨过程还包括了通过搅动或搅拌以防止被磨碎的组分不会再次压实。搅动或搅拌过程可以由熟练掌握搅拌方法以及搅拌机器的工人操作。一般来讲,搅动或搅拌速率为2转/分钟。搅动或搅拌速率也可低于或高于2转/分钟。被磨碎的组分处于不断的搅动或搅拌下已保证组分的可加工性。
研磨后,被磨碎的组分被传送或移装入一个工作槽或者容器中。传送或移装入工作槽或者容器的操作应该由熟练掌握相关方法及机器(例如运送机,传送带,滑轨等等)的工人进行从而保证被磨碎组分与分离组分的分配比例比较精确。
发明实施例示例中回收沥青的过程还包括将被磨碎组分与分离组分混合形成泥浆。其中,被磨碎组分与分离组分的分配比例约为2∶3到1000∶1,2∶3到500∶1,2∶3到100∶1,2∶3到10∶1,2∶3到3∶2,2∶3到3∶1或者1∶1。混合操作应该由熟练掌握相关方法及机器(例如混合器,搅拌器等等)的工人进行。混合在适当的工作槽中并采用2Hp混合器,工作槽中可盛装量为容器的一半。
发明中的分离组分可含有水溶助长剂和具备絮凝特性的分散剂。分离组分中还可以含有润湿剂。分离组分的pH可以约为7.0-8.5,分离组分的pH也可以约为7.4-8.5,7.4-7.8或者7.6-7.8。
对于发明实施例示例中的沥青回收过程中的具体条件,被磨碎组分与分离组分的加热温度需大于25℃(77°F);加热温度范围可以控制在约为32℃(90°F)-72℃(162°F)或是54℃(129°F)-60℃(140°F)。任何可将温度控制在工作范围内的常规的加热热源均可被采用。在加入被磨碎组分或者含有沥青的原料之前,分离组分通常被加热到约为77°F-162°F,100°F-150°F,130°F-140°F。
发明实施例示例中的沥青回收过程还包括了将泥浆高速搅拌形成泥浆混合物。泥浆可通过高速搅拌机器从工作槽中提取出或泵出。高速搅拌操作应该由熟练掌握相关方法及机器(例如搅拌器,研磨器,分散仪等等)的工人实施。高速搅拌可以通过带有一速率为每秒27米刀片的搅拌器实现。高速搅拌也可以通过带有几个速率为每秒27米刀片的搅拌器实现。高速搅拌器的刀片可以通过镀膜延长其寿命。镀膜可以选择不同的方法(例如,碳化钨镀膜,陶瓷镀膜等等)。
发明实施例示例中的泥浆在混合前先进行通气。在泥浆中通入空气可以使泥浆密度降低,更易于混合,而且有助于回收沥青过程中后期沥青的漂浮。
发明实施例示例中所指的高速搅拌可使用两种或几种搅拌速率。泥浆先在相对低的剪切力下混合(例如,刀片速率为每秒6英尺),这样可以使一部分砂土絮凝到混合物的底部而沉降。在某些情况下,至少50%的砂土会絮凝到底部。另外一些情况至少75%或者至少90%的砂土会絮凝到底部。这样底部的砂土被移走。砂土被断断续续的移走(即在连续搅拌泥浆的过程中)或者经过一定的累积,混合槽中泥浆被清空。残余的泥浆然后会在相对高的剪切力下混合。在“高剪切”的混合器中,大量的切力传递到被混合的物料中,这样的混合过程使得待分离物料的颗粒之间的切力相对短而高效(例如分离组分与含有沥青的原料之间)。高剪切力可以通过充分的搅拌或者振荡实现,经过充分的搅拌或振荡后的含有沥青的混合物料中的沥青颗粒被高剪切性或者高分散性的分离液所包溶,振荡时间不超过5分钟,泥浆温度大约为140°F,含有沥青原料中的99%沥青会从泥浆中分离出来,并且浮在体系的上层形成沥青层,而沥青层中的固体物(例如砂土和粘土)的含量不超过2%。类似的,任何可以将分离组分与油砂(或者其他含有沥青的物料,或者其他含有碳氢化合物的物料,或者其他物料)通过充分振荡形成高剪切力的常规仪器均可被选用,例如,高剪切混合机,高速研磨器,高速分散器,流化床,超声波混合仪,以及其他所有类似的可以提供在要求工作范围内充分振荡的常规仪器。此处,充分的振荡定义为经过振荡(或者混合)后的混合泥浆中的沥青颗粒被高剪切性或者高分散性的分离液所包溶,振荡时间不超过5分钟,泥浆温度大约为140°F,含有沥青的组分将有99%沥青会从泥浆中分离出来,并且浮在体系的上层形成沥青层,而沥青层中的固体物(例如砂土和粘土)的含量不超过2%。此处的高剪切定义为将混合物中所有颗粒物(包括颗粒度为5-200nm的颗粒)充分的机械分散,从而使得混合物中所有颗粒相互分离。这样的混合物呈单片状,尽管包含不同的成分但整体均匀,没有条纹状,水珠状;且易于区分像油砂这样含有碳氢化合物的凝聚团。多种速率混合使用可以延长搅拌机刀片的寿命。
发明实施例示例的回收沥青过程中还包括了将混合泥浆分离成至少三个分层,一层沥青,一层分离组分,一层固体物。高速搅拌的泥浆被转移或者释放到一个工作槽中或者一个容器中然后在此被分成三层。其中,沥青层浮在最上层,固体物质被絮凝到底层,分离组分层位于二者之间。一般来说,固体物质层基本由砂土和粘土组成。绝大部分固体物质层可以由熟练掌握相关方法及机器(例如运送机,传送带,浓缩机等等)的工人操作从工作槽或者容器的底部移走。
发明实施例示例的回收沥青过程中还包括了移取沥青层。绝大部分的沥青层可以由熟练掌握相关方法(例如撇去、倾倒、抽吸等等)及机器(例如带式撇油器,转鼓撇油器,吸油撇油器,抽吸器等等)的工人操作从工作槽或者容器中移取。移取沥青层的过程中还需要加热沥青(大约100°F至150°F),使得沥青保持一定的粘稠度从而易于由撇油器将其从工作槽或容器中移取。
一般来讲,移取的沥青仍含有不到2%的固体物质,沥青的粘稠度在140°F下约为4000到6000cps。有些情况下移取的沥青中含有不到1%的固体物质。
发明实施例示例的回收沥青过程中还包括净化或者二次回收过程,即将分离出的沥青层中的沥青再次加入分离组分形成二次混合物从而再次提炼沥青。二次混合中沥青与分离组分的配比例约为2∶3到1000∶1,2∶3到500∶1,2∶3到100∶1,2∶3到10∶1,2∶3到3∶2,2∶3到3∶1或者1∶1。二次混合应在高速搅拌以及高速剪切的条件下进行。高速搅拌可由熟练掌握相关方法及机器(例如搅拌器,磨碎机,分散仪等等)的工人进行。
通过回收沥青过程中的净化过程将第二次混合的物料又一次分离成至少三层,一层沥青,一层分离组分,一层固体物。其中,沥青层浮在最上层,固体物质被絮凝到底层,分离组分层位于二者之间。
第二次产生的固体物质层绝大部分可以由熟练掌握相关方法及机器(例如运送机,传送带,浓缩机,离心机等等)的工人操作从工作槽或者容器的底部移走。第二次产生的沥青层绝大部分可以由熟练掌握相关方法(例如撇去、倾倒、抽吸等等)及机器(例如带式撇油器,转鼓撇油器,吸油撇油器,抽吸器等等)的工人操作从工作槽或者容器的底部移走。移取沥青层的过程中还需要加热沥青(大约100°F至150°F),使得沥青保持一定的粘稠度从而易于由撇油器将其从工作槽或容器中移取。
在一个发明实施例示例中,在深度处理过程中含有沥青的组分将有99%沥青会从泥浆中分离出来,并且99%不含砂土和粘土。在另外一个发明实施例示例中,在深度处理过程中含有沥青的组分将至少有98%或者97%沥青会从泥浆中分离出来,并且99%不含砂土和粘土。在另外一些发明实施例示例中,在深度处理过程中含有沥青的组分将至少有99.5%沥青会从泥浆中分离出来,并且99%的不含砂土和粘土。
在一个发明实施例示例中,沥青回收模型过程包括从分离组分层或者二次分离组分层中回收分离组分。回收的分离组分可以在沥青回收过程中与含有组分的沥青混合使用。
在一个发明实施例示例中,沥青回收模型过程是一个连续过程。在另一个发明实施例示例中,沥青回收模型过程是一个循环过程。
发明实施例示例在实验室和试验工厂规模的结果中得到了很好的体现。我们这里讨论的结果应该是为了要体现获得油砂的过程,从油砂中萃取沥青的过程,以及沥青的后续处理过程。举例来说,用挖掘铲开采油砂矿石,装载到卡车上或者其他交通工具。卡车把油砂运到粉碎机,将油砂粉碎。将碾碎的油砂加入到混合罐中与如下探讨的其他分离组分一起混合。分离的沥青被抽取储存起来,可进一步精炼制成原油来作为生产液态汽车燃料,民间燃料用油和其他石油化学产品的原料。
以下这些例子是为了从不同方面进行阐述,而不是仅仅局限于这些方面。
例1(a)从阿沙巴斯克油砂中分离沥青
Figure BPA00001545693600161
将300克的阿沙巴斯克油砂加入到装有分离组分(见表1a)的烧杯中,加热到54℃至60℃。将一高剪切实验室搅拌器放入烧杯中,以3500转/分钟的速度搅拌3分钟。移出搅拌器,在接下来的5-30分钟的过程中,会观察到发生清晰完整的四相分离。顶层即是第一层含有沥青,第二层中含有分离组分,第三层中含有粘土,底层也即是第四层中含有砂土及其它颗粒物质。
从烧杯中移出沥青后,冷却剩余的混合物。检测沥青的纯度,大于99%,砂土和粘土等杂质含量很少。大约可以回收45g的沥青,大于99%的油砂样品中能够提供的沥青。
砂土也被回收,检测得到沥青等的杂质含量很少,纯度大于99%。将砂土置于72℃的干燥箱中保持8个小时,冷却至室温后,就可以用20-25目的筛子筛选。
为了进一步确定残留在砂土中沥青的含量,将100.00g干燥的砂土置于烧杯中,再加入100g甲苯,混合搅拌,静置。将甲苯轻轻倒出,肉眼可观察到甲苯溶液很澄清。将砂土重新在72℃下干燥8小时蒸发残留的甲苯,之后称量,剩余砂土重99.86g。
在另一个1升的烧杯中加入300克新制备的等分试样的分离组分,再加入45克分离回收得到的沥青。将以上混合物加热到72℃,以2000转/分钟的转速搅拌3分钟。冷却静置,按上述步骤分离。分离得到的沥青则完全不含杂质。
在原先的1升烧杯中分离沥青之后,移出分离组分。将275克这样的分离组分加入到1升烧杯中,再加入275g新的阿沙巴斯克油砂等分试样。将混合得到的泥浆加热到72℃,以3000转/分钟的速度搅拌3分钟。
从烧杯中移出沥青后,冷却剩余的混合物。检测沥青的纯度,大于99%,砂土和粘土等杂质含量很少。大约可以回收41克的沥青,大于99%的油砂样品中能够提供的沥青。
砂土也被回收,检测得到沥青等的杂质含量很少,纯度大于99%。将砂土置于72℃的干燥箱中保持8个小时,冷却至室温后,就可以用20-25目的筛子筛选。
为了进一步确定残留在砂土中沥青的含量,将100.00g干燥的砂土置于烧杯中,再加入100g甲苯,混合搅拌,静置。将甲苯轻轻倒出,肉眼可观察到甲苯溶液很澄清。将砂土重新在72℃下干燥8小时蒸发残留的甲苯,之后称量,剩余砂土重99.83g。
例1(b)从阿沙巴斯克油砂中分离沥青
制备300g下述的分离组分,装入1L的烧杯中。
组分1(b)
Figure BPA00001545693600171
将300g的阿沙巴斯克油砂加入到装有分离组分(见表1b)的烧杯中,加热到54℃至60℃。将一高剪切实验室搅拌器放入烧杯中,以3500转/分钟的速度搅拌3分钟。移出搅拌器,在接下来的5-30分钟的过程中,会观察到发生清晰完整的四相分离。顶层即是第一层含有沥青,第二层中含有分离组分,第三层中含有粘土,底层也即是第四层中含有砂土及其它颗粒物质。
用药匙(也可使用其他物理分离方法,例如倾倒,注射器或者抽吸器)从烧杯中移出沥青后,冷却剩余的混合物。检测沥青的纯度大于99%,砂土和粘土等杂质含量很少。大约可以回收45g的沥青,大于99%的油砂样品中能够提供的沥青。
砂土也被回收,检测得到沥青等的杂质含量很少,纯度大于99%。将砂土置于72℃的干燥箱中保持8个小时,冷却至室温后,就可以用20-25目的筛子筛选。
为了进一步确定残留在砂土中沥青的含量,将255g干燥的砂土置于烧杯中,再加入255g甲苯,混合搅拌,静置。将甲苯轻轻倒出,肉眼可观察到甲苯溶液很澄清。将砂土重新在72℃下干燥8小时蒸发残留的甲苯,之后称量,剩余砂土重255g。
例2(a)从阿沙巴斯克尾矿池中分离沥青
制备200g例1(a)中的分离组分,将300g阿沙巴斯克尾矿池的矿渣加入到装有上述分离组分的1L烧杯中,加热到72℃,以3000转/分钟的速度搅拌2分钟。移出搅拌器,在接下来的5-30分钟的过程中,会观察到发生清晰完整的四相分离。顶层即是第一层含有沥青,第二层中含有分离组分,第三层中含有粘土,底层也即是第四层中含有砂土及其它颗粒物质。
从烧杯中移出沥青后,冷却剩余的混合物。检测沥青的纯度,大于99%,砂土和粘土等杂质含量很少。大约可以回收12g的沥青,大于99%的矿渣样品中能够提供的沥青。
砂土也被回收,检测得到沥青等的杂质含量很少,纯度大于99%。将砂土置于72℃的干燥箱中保持8个小时,冷却至室温后,就可以用20-25目的筛子筛选。
为了进一步确定残留在砂土中沥青的含量,将100.00g干燥的砂土置于烧杯中,再加入100g甲苯,混合搅拌,静置。将甲苯轻轻倒出,肉眼可观察到甲苯溶液很澄清。将砂土重新在72℃下干燥8小时蒸发残留的甲苯,之后称量,剩余砂土重99.76g。
例2(b)从犹他州油砂中分离沥青
制备300g下述的分离组分,装入1L的烧杯中。
组分2(b)
Figure BPA00001545693600181
Figure BPA00001545693600191
将300g的犹他州油砂加入到装有分离组分(见表2b)的烧杯中,加热到54℃至60℃。将一高剪切实验室搅拌器放入烧杯中,以3500转/分钟的速度搅拌3分钟。移出搅拌器,在接下来的5-30分钟的过程中,会观察到发生清晰完整的四相分离。顶层即是第一层含有沥青,第二层中含有分离组分,第三层中含有粘土,底层也即是第四层中含有砂土及其它颗粒物质。
用药匙(也可使用其他物理分离方法,例如倾倒,注射器或者抽吸器)从烧杯中移出沥青后,冷却剩余的混合物。检测沥青的纯度大于99%,砂土和粘土等杂质含量很少。大约可以回收40g的沥青,大于99%的油砂样品中能够提供的沥青。
砂土也被回收,检测得到沥青等的杂质含量很少,纯度大于99%。将砂土置于72℃的干燥箱中保持8个小时,冷却至室温后,就可以用20-25目的筛子筛选。
为了进一步确定残留在砂土中沥青的含量,将266g干燥的砂土置于烧杯中,再加入266g甲苯,混合搅拌,静置。将甲苯轻轻倒出,肉眼可观察到甲苯溶液很澄清。将砂土重新在72℃下干燥8小时蒸发残留的甲苯,之后称量,剩余砂土重266g。
例2(c)从犹他州油砂尾矿池中分离沥青
制备300g例1(a)中的分离组分,将300g犹他州油砂尾矿池的矿渣加入到装有上述分离组分的1L烧杯中,加热到72℃,以3000转/分钟的速度搅拌3分钟。移出搅拌器,在接下来的5-30分钟的过程中,会观察到发生清晰完整的四相分离。顶层即是第一层含有沥青,第二层中含有分离组分,第三层中含有粘土,底层也即是第四层中含有砂土及其它颗粒物质。
从烧杯中移出沥青后,冷却剩余的混合物。检测沥青的纯度,大于99%,砂土和粘土等杂质含量很少。大约可以回收4g的沥青,大于99%的矿渣样品中能够提供的沥青。
砂土也被回收,检测得到沥青等的杂质含量很少,纯度大于99%。将砂土置于72℃的干燥箱中保持8个小时,冷却至室温后,就可以用20-25目的筛子筛选。
为了进一步确定残留在砂土中沥青的含量,将100.00g干燥的砂土置于烧杯中,再加入100g甲苯,混合搅拌,静置。将甲苯轻轻倒出,肉眼可观察到甲苯溶液很澄清。将砂土重新在72℃下干燥8小时蒸发残留的甲苯,之后称量,剩余砂土重99.77g。
例2(d)从犹他州油砂中分离沥青
将300g的犹他州油砂加入到装有300g分离组分(见表1a)的1L烧杯中,加热到54℃至60℃。将一高剪切实验室搅拌器放入烧杯中,以3500转/分钟的速度搅拌3分钟。移出搅拌器,在接下来的5-30分钟的过程中,会观察到发生清晰完整的四相分离。顶层即是第一层含有沥青,第二层中含有分离组分,第三层中含有粘土,底层也即是第四层中含有砂土及其它颗粒物质。
从烧杯中移出沥青后,冷却剩余的混合物。检测沥青的纯度,大于99%,砂土和粘土等杂质含量很少。大约可以回收40g的沥青,大于99%的油砂样品中能够提供的沥青。
砂土也被回收,检测得到沥青等的杂质含量很少,纯度大于99%。将砂土置于72℃的干燥箱中保持8个小时,冷却至室温后,就可以用20-25目的筛子筛选。
在另一个1升的烧杯中加入300g新制备的等分试样的分离组分,再加入40g分离回收得到的沥青。将以上混合物加热到72℃,以2000转/分钟的转速搅拌3分钟。冷却静置,按上述步骤分离。分离得到的沥青则完全不含杂质。
在第一个1升烧杯中分离沥青之后,移出原始分离组分。将275克这样的分离组分加入到一个1升烧杯中,再加入275克新的犹他州油砂等分试样。将混合得到的泥浆加热到72℃,以3000转/分钟的速度搅拌3分钟。移出搅拌器,在接下来的5-30分钟的过程中,会观察到发生清晰完整的四相分离。顶层即是第一层含有沥青,第二层中含有分离组分,第三层中含有粘土,底层也即是第四层中含有砂土及其它颗粒物质。
从烧杯中移出沥青后,冷却剩余的混合物。检测沥青的纯度,大于99%,砂土和粘土等杂质含量很少。大约可以回收44克的沥青,大于99%的油砂样品中能够提供的沥青。
砂土也被回收,检测得到沥青等的杂质含量很少,纯度大于99%。将砂土置于72℃的干燥箱中保持8个小时,冷却至室温后,就可以用20-25目的筛子筛选。
为了进一步确定残留在砂土中沥青的含量,将100.00克干燥的砂土置于烧杯中,再加入100克甲苯,混合搅拌,静置。将甲苯轻轻倒出,肉眼可观察到甲苯溶液很澄清。将砂土重新在72℃下干燥8小时蒸发残留的甲苯,之后称量,剩余砂土重99.85克。
例3用河水制备分离组分。
河水来自于坐落在加拿大阿尔伯塔省北部的阿沙巴斯克。按照标准配方(见下表3)用河水制备了800克分离组分。用210克该分离组分和90克加拿大油砂(来自加拿大阿尔伯塔省北部阿沙巴斯克地区)混合。在和加拿大油砂混合之前,分离组分的pH值应用磷酸调至7.76。
将分离组分和加拿大油砂的混合物放入有金属螺盖的玻璃瓶中。用微波炉将样品加热到140°F(约61℃)。加热后,为了分散混合物,须采用配置“1”刀片的10,000转/分钟高速分散器。一台Premier Mill公司的,2000系列,2000型号,110V电压,1马力功率,12安培台式分散器被选为该高速分散器。分散器工作大约3分钟。之后,样品组分沉降,显著分层。半小时后,溶液显著分为三层,沥青在顶层,分离组分在第二层,固体(砂土和粘土)在第三层。考虑到溶液显著分为三层,我们用去离子水做的控制对比实验的结果表明,在制备分离组分的过程中,用未经预处理的河水是可以接受的。
在玻璃瓶中的混合物冷却之后,溶液显著分为三层(大约1小时),用药匙(也可使用其他物理分离方法,例如倾倒,注射器或者抽吸器)从玻璃瓶中移出沥青。检测沥青的纯度大于99%,砂土和粘土等杂质含量很少。大约可以回收9克的沥青,大于99%的加拿大油砂样品中的沥青含量。
Figure BPA00001545693600221
例4用工艺用水制备分离组分。
在阿沙巴斯克油砂工艺中的用水(又称循环水)取自加拿大。该工艺用水呈棕褐色,有泥沙悬浮。按表1(b)中提供的标准配方用工艺用水制备了800克的分离组分。将分离组分静置一小时,让工艺用水中的大部分粘土絮凝沉淀后,将分离组分溶液倾倒出来。然后(用磷酸)将溶液pH值调至7.76。用210克该分离组分和90克加拿大油砂(来自加拿大阿尔伯塔省北部阿沙巴斯克地区)混合。
将分离组分和加拿大油砂的混合物放入有金属螺盖的玻璃瓶中。用微波炉将样品加热到140°F(约61℃)。加热后,为了分散混合物,须采用配置1”刀片的10,000转/分钟高速分散器。一台Premier Mill公司的,2000系列,2000型号,110V电压,1马力功率,12安培台式分散器被选为该高速分散器。分散器工作大约3分钟。之后,样品组分沉降,显著分层。半小时后,溶液显著分为三层,沥青在顶层,分离组分在第二层,固体(砂土和粘土)在第三层。实验的结果表明,在制备分离组分的过程中,用未经预处理的工艺用水是可以接受的。
在玻璃瓶中的混合物冷却之后,溶液显著分为三层(大约1小时),用药匙(也可使用其他物理分离方法,例如倾倒,注射器或者抽吸器)从玻璃瓶中移出沥青。检测沥青的纯度大于99%,砂土和粘土等杂质含量很少。大约可以回收9克的沥青,大于99%加拿大油砂样品中的沥青含量。
例5从MFT(成熟精细尾矿30%矿样)尾矿池中分离沥青。
参照上述例3,用河水制备了800克分离组分。矿渣样品取自坐落在加拿大阿尔伯塔省北部的阿沙巴斯克地区的一个尾矿池,记做MFT矿样。一般来说,成熟精细的尾矿由固体(比如砂土和粘土)悬浮液,沥青和水组成,并且可按矿龄分类(比如10年,20年,30年,40年)。MFT矿样含有约30%的固体(砂土,粘土和沥青)和约70%的水。厚重,粘稠,黑色,并有刺激性气味(被认为是与厌氧细菌的存在有关)。我们再一次用210克分离组分和90克MFT矿样混合。在和加拿大油砂混合之前,分离组分的pH值应用磷酸调至7.8。
将分离组分和加拿大油砂的混合物放入有金属螺盖的玻璃瓶中。用微波炉将样品加热到140°F(约61℃)。加热后,为了分散混合物,须采用配置1”刀片的10,000转/分钟的高速分散器。一台Premier Mill公司的,2000系列,2000型号,110V电压,1马力功率,12安培台式分散器被选为该高速分散器。分散器工作大约3分钟。
之后,样品组分沉降,15分钟之后开始分层。半小时后,溶液显著分为三层,沥青在顶层,分离组分在第二层,固体(砂土和粘土)在第三层。与例4,例5相比,固体的完全沉降和溶液的显著分层花费了更长时间是因为MFT矿样中的固体(如粘土)含量的关系。
当玻璃瓶中的物质冷却并分层后(约耗时12小时),用药匙将沥青从玻璃瓶中取出(也可使用其他物理分离手段,如倾倒,注射器吸取或其抽吸装置)。此时,沥青的纯度大于99%,仅含少量的沙土和粘土等杂质。回收的沥青质量大约是2.8克,这意味在加拿大油砂样品中,99%的沥青已被回收。
示例6——可循环的沥青回收工艺
一个规模可变化的沥青回收系统已经建成并成功回收了加拿大油砂中99%以上的沥青。
这个过程的第一步是要将油砂磨到适当的大小以便后续机械步骤的操作。磨削的过程是由造粒机完成的。为了防止油砂被压实,在搅拌器上以约2转/分钟和15000ft·pounds的扭矩搅拌油砂。搅拌器底部的液压输送机将油砂输送到浆池,浆池里有按照表3所示配比配好的pH在7.4到7.8的分离组分。浆池是一个400加仑的油箱,混合物只装到池子的一半,以促进良好的混合。用蒸汽热交换器将浆槽中的油砂和分离组分加热到大约140°F。用功率为2马力的搅拌机(由赖特宁公司制造)将油砂和和分离组分按1∶1混合。这是一个连续的操作流程。渣浆泵的运行速度是22-23加仑/分钟。浆池里的渣浆体积保持在220加仑左右。(因此,浆料的平均停留时间约为10分钟)。
接着,将泥浆抽(使用戴明型# 400110400 7.5马力泵,并配备了6英寸的叶轮,转速为1720转/分钟)到由两个50升容器组成的研磨分散机(由赖特宁公司制造)中。泥浆以22-23加仑/分钟的速度被送入容器。每个容器都有两个直径为12英寸的刀片。以20cf/Hr的速度给混合后的泥浆充气。用蒸汽热交换器加热使泥浆的温度保持在约140°F。然后将泥浆以1750转/分钟,27米/秒的叶尖速度进行搅拌。研磨分散后的浆液排放到研磨分散机的另一个容器里,也即是主要的分离器。这个容器是一个3000加仑的长方形油箱。浆液在此沉淀分离。
几乎是在浆液进入主分离器后,沥青就立即浮到罐顶。相对较短的时间内(例如,约20分钟),泥浆即分成三个层浆----沥青层,分离组分层,和固体层(在这个实例中,固体层可能包括已分离的砂土层和黏土层)。固体层(主要由砂土和粘土组成)往往絮凝在水箱底部,分离器底部的传送带将容器底积聚的固体运走。沥青混合物中,至少有99%的沥青可以在五分钟内被分离出来并且浮到顶层。
浆液一进入主分离器,沥青层就立马被分离并且漂浮到罐顶。一旦沥青层在灌顶形成,带状撇油器就将其带离体系。被分离的沥青在140°F时的粘度在4000至6000CPS之间。撇油器中的加热设备通过控制温度使得沥青有足够的粘度以便运输(例如,温度在100°F---150°F之间)。分离后的沥青中固体杂质的质量分数(如砂土和粘土)少于2%。
分离得到的沥青以2∶3的比例再次和额外的分离组分混合。将混合物抽到一个含四个叶片的双层堆叠式研磨分散机中。蒸汽热交换剂将混合物的温度维持在140°F。将研磨分散后的混合物排到第二分离器中并在此进行分离。第二分离器是一个200加仑的长方形罐。
混合物分离成三个单独的层,分别为沥青层,分离组分层,和固体层。固体层絮凝在水箱底部。浆液一进入分离器,沥青层就立马被分离并且漂浮到罐顶。撇油器将沥青分离。被分离的沥青占油砂中沥青含量的99%以上。通过标准的现场检测方法,发现沥青的纯度大于99%,仅含少量的砂土、粘土等杂质。
第二分离器的分离组分可以回流到主分离器中以实现分离组分的循环利用。
示例7-阿萨巴斯卡油砂中沥青的分离
在含有分离组分的烧杯中加入300克阿萨巴斯卡油砂.由此得到的泥浆被加热到54℃至60℃。将高剪切混合器放进烧杯并以3500转/分钟的速度搅拌3分钟。然后将搅拌器移开。在接下来的3--50分钟里,玻璃杯里发生相分离现象,出现了四个单独的相。第一层是沥青层,第二层是分离组分层,第三层是黏土层,第四层是砂土和其他物质。
配方7
Figure BPA00001545693600251
逐渐冷却玻璃杯中的物质,同时,沥青也被分离出来。分离得到的沥青纯度大于99%,仅含少量的砂土、粘土等杂质。大约有45克的沥青被回收,这意味着油砂样品中99%以上的沥青已被分离出来。
同时,砂土也被回收,残留的沥青量少于1%。将砂土放置在72℃烘箱干燥8小时,冷却至室温后,就可以用20-25目的筛子筛选。
为了进一步测定砂土中残留的沥青量,将100.00克干燥的砂土放入烧杯,加入100克甲苯,搅拌,然后静置一段时间。分层后,将上层清澈的甲苯倒出。砂土在72℃下干燥8小时以挥发残留在表面的甲苯。之后称重,可得到大约99.8克的砂土。
除非特别声明外,说明书以及权利要求里的参数值是可以根据特殊情况在规范要求的范围内进行更改的。并不是要限制该方法的运用范围,但每个参数至少应该根据报道的有效位数和四舍五入原则来设定。
为了扩大运用范围,我们给出的数值范围和参数值都是粗略值。但是在具体的实例中,数值还是尽可能地精确。然而,在每个实验测试中,由于偶然误差的存在,每个数值都固然有些偏差。
此外,尽管通过示例详细地描述了体系、方法等,也清楚地描述了示例的细节,但这并不是意味着使用时需要限制到这些细节。当然,为了描述清楚体系和方法而将每个可能的成分组合和方法组合都列举出来是不可能的。熟练操作后将会发现这个方法的其他优势并改进不足之处。因此,广义来讲,这项发明不是局限于特殊的事例以及上面所举的例子。因此,只要没有偏离这个发明的基本原则和原理,就可以运用这项发明实施例解决问题。所以,这项发明实施例囊括了在附加权利要求范围内的修改和变化。前面的叙述并不是为了限制发明实施例的范围,而是为了说明该项专利的范围是由权利要求内容及其相似条约来界定的。
最后,从一定范围上讲,细节描述和权利要求中使用的术语“包括”是可兼的,和连词“包括”表达的意思类似。所以,权利要求中的术语“或者”(例如A或者B)表达意思的是或者A或者B或者AB两者。如果想表达“或者A或者B但没有AB两者”那么应该使用术语“只有A或者只有B但不是二者都有”。相似地,如果要表达“有且仅有A,B,C中的一个”那么应该使用术语“有且仅有”。因此,术语“或者”在此是可兼的,详见Bryan A.Garner,A Dictionary ofModern Legal Usage((2d.Ed.1995).字典624页。

Claims (72)

1.用分离组分分离回收沥青混合物中的沥青回收工艺,主要包括以下过程:
a.将沥青混合物和分离组分混合,得到泥浆;
b.在高速高剪切混合器中充分搅拌,得到混合均匀的泥浆;
c.混合后的泥浆至少分为三层——一次沥青层,一次分离组分层,一次固体层;
d.回收一次沥青层;
e.将回收得到的沥青再次和额外的分离组分混合得到沥青混合物;
f.混合后的沥青混合物至少分为三层——二次沥青层,二次分离组分层,二次固体层;
g.回收二次沥青层;
h.一次沥青层含的粘土和砂粒质量分数小于2%,二次沥青层回收率高于99%且纯度高于99%,不含粘土和砂粒。
2.根据权利要求1的工艺,其中,分离组分的pH在7-8.5之间,成分有:亲水助剂,凝絮状分散剂,和润湿剂(可选)。
3.根据权利要求1的工艺,其中,沥青混合物包括油砂,尾矿,工艺水,淤泥,或者它们的混合物。
4.根据权利要求1的工艺,其中,沥青混合物的主要成分是油砂。
5.根据权利要求1的工艺,其中,在混合分离组分前,需要将沥青混和物磨细。
6.根据权利要求1的工艺,其中,用传输装置将沥青混合物传送到一个容器里,并在此容器里将混合物和分离组分混合。
7.根据权利要求1的工艺,其中,分离组分和沥青混和物的比例在3∶1到1∶1之间。
8.根据权利要求1的工艺,其中,高速混合是通过一台末端速度至少为27米/秒的叶片式混合器实现的。
9.根据权利要求8的工艺,其中,混合器叶片表面涂有一层由碳化钨,陶瓷或者它们的混合物组成的覆盖层。
10.根据权利要求1的工艺,其中,要给混合后的泥浆鼓气。
11.根据权利要求1的工艺,其中,用传输设备运送一次固体层。
12.根据权利要求1的工艺,其中,一次固体层和二次固体层基本是由砂土和粘土组成。
13.根据权利要求1的工艺,其中,泥浆会分层并且固体会凝絮下来。
14.根据权利要求1的工艺,其中,粘土含量少于2%的一次沥青层在140°F时的粘度在4000到6000cps之间。
15.根据权利要求1的工艺,其中,用撇油器回收一次沥青层。
16.根据权利要求15的工艺,其中,撇油器需加热。
17.根据权利要求1的工艺,其中,一次沥青层被转移至一个分离容器中并被加热到至少140°F。
18.根据权利要求1的工艺,其中,一次沥青层和分离组分的混合比在3∶1到1∶1之间。
19.根据权利要求1的工艺,其中,用撇油器回收二次沥青层。
20.根据权利要求19的工艺,其中,撇油器需加热。
21.根据权利要求1的工艺,其中,二次分离组分层是可循环使用的,可以再次分离沥青混合物。
22.根据权利要求1的工艺,其中,在和油砂组分混合之前,需要将分离组分加热到100°F到150°F之间。
23.根据权利要求1的工艺,其中的工艺是一个连续的过程。
24.根据权利要求1的工艺,其中的工艺是一个分批处理的过程。
25.根据权利要求1的工艺,其中,在高速搅拌之前,至少要保证泥浆中75%的砂土已经沉淀下来。
26.使用分离组分分离沥青混合物中的沥青的工艺,主要包括以下过程:
a.将沥青混合物和分离组分混合,得到泥浆;
b.在高速高剪切混合器中充分搅拌,得到均匀的泥浆;
c.混合后的泥浆至少分为三层---沥青层,分离组分层,固体层;
d.回收沥青层;
沥青层含的粘土和粘土质量分数小于2%。
27.根据权利要求26的工艺,其中,分离组分的pH大于7.5,成分有:亲水助剂,凝絮状分散剂和润湿剂(可选)。
28.根据权利要求26的工艺,其中,沥青混合物包括油砂,尾矿,工艺水,淤泥,或者它们的混合物。
29.根据权利要求26的工艺,其中,沥青混合物主要成分是油砂。
30.权利要求26的工艺,其中,在和分离组分混合前,需要将沥青混合物磨细。
31.根据权利要求26的工艺,其中,用传输装置将沥青混合物传送到一个容器里,并在此容器里和分离组分混合。
32.根据权利要求26的工艺,其中,分离组分和沥青混合物的比例在3∶1到1∶1之间。
33.根据权利要求26的工艺,其中,用一台末端速度至少为27米/秒的叶片式混合器高速混合混合物。
34.根据权利要求33的工艺,其中,混合器叶片表面涂有一层由碳化钨,陶瓷或者它们的混合物组成的盖层。
35.根据权利要求26的工艺,其中,要给混合的泥浆鼓气。
36.根据权利要求26的工艺,其中,用传输设备运送固体层。
37.根据权利要求26的工艺,其中,固体层主要是由砂土和粘土组成。
38.根据权利要求26的工艺,其中,泥浆会分层并且固体会凝絮下来。
39.根据权利要求26的工艺,其中,粘土含量少于2%的沥青层在140°F时的粘度在4000-6000cps之间
40.根据权利要求26的工艺,其中,用撇油器回收沥青层。
41.根据权利要求40的工艺,其中,撇油器需加热。
42.根据权利要求26的工艺,其中,沥青层被转移至一个分离容器中并被加热到至少140°F。
43.根据权利要求26的工艺,其中,回收的沥青层和分离组分的混合比在3∶1到1∶1之间。
44.根据权利要求26的工艺,其中,分离组分层是可循环使用的,可以再次用于分离沥青混合物。
45.根据权利要求26的工艺,其中,在和油砂组分混合之前,需要将分离组分加热到100°F到150°F之间。
46.根据权利要求26的工艺,该工艺是一个连续的过程。
47.根据权利要求26的工艺,该工艺是一个分批处理的过程.
48.根据权利要求26的工艺,其中,高速搅拌之前,至少要保证泥浆中75%的砂土已经沉淀下来。
49.使用分离组分分离沥青混合物中的沥青的工艺,主要包括以下过程:
a.将沥青混合物和分离组分混合,得到泥浆。
b.将泥浆静置一段时间,以确保在高速搅拌之前,泥浆中至少75%的砂土已经沉淀下来。
c.在高速高剪切剪混合器中充分搅拌,得到混合均匀的泥浆;
d.混合后的泥浆分为至少三层——一次沥青层,一次分离组分层,一次固体层;
e.回收一次沥青层;
f.将回收得到的一次沥青层和额外的分离组分混合得到沥青混合物;
g.混合后的混合物静置后至少分为三层——二次沥青层,二次分离组分层,二次固体层;
h.回收二次沥青层;
此时,一次沥青层含的粘土和砂粒质量分数小于2%,二次沥青层回收率高于99%且纯度高于99%;
分离组分的pH在7到8.5之间,成分及质量比如下:亲水助剂0.1~4.0%,凝絮状分散剂0.25~4.5%,强酸1.7~8.6%,碱2~9.5%。有时可以选择性地加入润湿剂。
50.根据权利要求49的工艺,其中,沥青混和物包括油砂,尾矿,工艺水,淤泥,或者其混合物。
51.根据权利要求49的工艺,其中,沥青混和物的主要成分是油砂。
52.根据权利要求49的工艺,其中,在混合分离组分前,需要将沥青混合物磨细。
53.根据权利要求49的工艺,其中,用传输装置将沥青混合物传送到一个容器里,并在此容器里和分离组分混合。
54.根据权利要求49的工艺,其中,分离组分和沥青混合物的比例在3∶1到1∶1之间。
55.根据权利要求49的工艺,其中,高速混合是通过一台末端速度至少为27米/秒的叶片式混合器实现的。
56.根据权利要求55的工艺,其中,混合器叶片表面涂有一层由碳化钨,陶瓷或者它们的混合物组成的盖层。
57.根据权利要求49的工艺,其中,要给混合的泥浆鼓气。
58.根据权利要求49的工艺,其中,用传输设备运送固体层。
59.根据权利要求49的工艺,其中,固体层主要是由砂土和粘土组成。
60.根据权利要求49的工艺,其中,泥浆会分层并且固体会凝絮下来。
61.根据权利要求49的工艺,其中,粘土含量少于2%的沥青层在140°F时的粘度在4000to 6000cps之间。
62.根据权利要求49的工艺,其中,用带状乳油器回收一次沥青层。
63.根据权利要求49的工艺,其中,撇油器需要加热。
64.根据权利要求49的工艺,其中,沥青层被转移至一个分离容器中并被加热到至少140°F。
65.根据权利要求49的工艺,其中,回收的沥青层和分离组分的混合比在3∶1到1∶1之间。
66.根据权利要求49的工艺,其中,用带状撇油器回收二次沥青层。
67.根据权利要求66的工艺,其中,撇油器需要加热。
68.根据权利要求49的工艺,其中,分离组分层是可循环使用的,可以再次用于分离沥青混合物。
69.根据权利要求49的工艺,其中,在和油砂组分混合之前,需要将分离组分加热到100°F到150°F之间。
70.根据权利要求49中的工艺,该工艺是一个连续的过程。
71.根据权利要求49中的工艺,该工艺是一个分批处理的过程。
72.根据权利要求49的工艺,其中,高速搅拌之前,至少要保证泥浆中75%的砂土已经沉淀下来。
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