CN112076804A - 一种重质馏分油加氢处理催化剂再生复活方法 - Google Patents
一种重质馏分油加氢处理催化剂再生复活方法 Download PDFInfo
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- 238000004073 vulcanization Methods 0.000 description 4
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- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 3
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
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- KYQODXQIAJFKPH-UHFFFAOYSA-N diazanium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [NH4+].[NH4+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O KYQODXQIAJFKPH-UHFFFAOYSA-N 0.000 description 1
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 1
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- B01J38/00—Regeneration or reactivation of catalysts, in general
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/28—Regeneration or reactivation
- B01J27/30—Regeneration or reactivation of catalysts comprising compounds of sulfur, selenium or tellurium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/485—Impregnating or reimpregnating with, or deposition of metal compounds or catalytically active elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
- B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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Abstract
本发明涉及一种重质馏分油加氢处理催化剂再生复活方法,所述方法为再生后催化剂置于含无机助剂、有机螯合配体助剂的溶液中,在声场条件下进行浸渍;浸渍后的样品室温晾干;再经两步热处理得到活化的催化剂。本发明增大再生后催化剂的有效比表面积,提高活性组分分散度,经过该方法处理再生后的催化剂,硫化度高,活性相数目增加,提高了催化剂的反应活性,本方法催化剂复活过程中无氨氮排放,不污染环境。
Description
技术领域
本发明属于催化剂再生复活领域,具体涉及一种重质馏分油加氢处理催化剂再生复活方法。
背景技术
石油馏分的加氢处理过程是生产清洁燃料的有效手段之一,其核心是加氢处理催化剂。在长期使用过程中,催化剂表面因发生缩合、脱氢等化学反应,形成了大分子含碳化合物,覆盖了催化剂活性中心,减少了催化剂反应的有效表面积,最终使催化剂完全失去活性。通过再生-复活手段,使旧催化剂进行活性恢复,减少旧催化剂的处理,降低炼厂运行成本,保护了环境,具有一定的社会效益和经济效益。
加氢处理催化剂含有周期表中第Ⅷ族及第ⅥB族的活性组分氧化物负载到载体中,载体一般含有氧化铝、氧化硅、二氧化钛、氧化锆等。通过浸渍工艺流程,将活性组分浸渍到载体上,再经过干燥和焙烧工序制备出成品催化剂。
催化剂再生方式分为两种器内再生和器外再生。目前工业上全部采用器外再生技术,其优点是催化剂再生过程中不易产生局部过热,活性恢复好。
工业上使用的器外再生方法主要是催化剂在窑炉内与氧气接触,除去催化剂表面的生成的硫、碳,即通过烧硫、烧碳的方式使催化剂再生。与新鲜催化剂相比,再生催化剂不但孔容、比表面下降,活性的下降幅度也很大,为了提高再生后催化剂的反应活性,必须对再生催化剂进行活性恢复,使其使用性能接近新鲜催化剂的水平。
大量文献专利中也阐述了一些对再生剂活性恢复的方法。美国专利US7087546B2报道了一种添加剂基催化剂的再生和活性恢复方法,该方法包括将使用过的旧催化剂在氧气条件下,经过温度不超过500℃再生后,将有机添加物引入催化剂内,必要情况下可将50%的添加剂存留于催化剂中,之后进行干燥。通常干燥温度控制在200℃以下。所述有机添加物选自含有至少两个氧原子和2~10个碳原子的化合物或其醚类、或者含有至少一个共价键氮原子和至少一个羰基的化合物。
美国专利US6239054B1公开了一种采用配体化合物处理失活催化剂该方法包括用乙二胺四乙酸二铵(EDTA)浸渍工业再生后的失活催化剂,之后在60℃下密闭容器中老化4天,最后进行干燥和焙烧。焙烧过程中有氨氮化合物放出,对环境造成污染。
中国专利CN1921942A报道了一种恢复失效加氢处理催化剂活性的方法,包括将积碳的失效加氢处理催化剂进行烧炭处理,得到碳含量降低至0.5~2.5总量%的中间催化剂,将该中间催化剂与含氮的螯合剂溶液进行接触和老化处理,其中老化处理时间超过10小时,最后经干燥处理得到再生的催化剂,其中所引入螯合剂量的50%以上保留在干燥后的催化剂中。催化剂在干燥过程中有氨氮化合物放出,对环境造成一定的污染。
发明内容
本发明提供一种重质馏分油加氢处理催化剂再生复活方法,增大再生后催化剂的有效比表面积,提高活性组分分散度。经过该方法处理再生后的催化剂,硫化度高,活性相数目增加,提高了催化剂的反应活性。本方法催化剂复活过程中无氨氮排放,不污染环境。
本发明所采用的技术方案是:
一种重质馏分油加氢处理催化剂再生复活方法,所述方法包括以下步骤:
1)再生后催化剂置于含无机助剂、有机螯合配体助剂的溶液中,在声场条件下进行浸渍;
2)浸渍后的样品室温晾干;
3)晾干后的样品经两步热处理得到活化的催化剂。
优选地,所述步骤1)无机助剂为含有P、Si物质的一种或几种组合,其中含P的物质为磷酸,含Si的物质为羟基硅油或羧基硅油或其他。
优选地,所述步骤1)有机螯合配体助剂为含羟基化合物或羧基化合物的或其组合。
进一步优选地,所述羟基化合物为丙三醇、丁二醇、山梨糖醇、聚乙二醇、聚丁烯醇、二乙二醇、三缩二乙二醇、乙二醇中的一种或多种的组合。
进一步优选地,所述羧酸类化合物为草酸、酒石酸、柠檬酸、苹果酸、水杨酸、D-葡萄糖、乳酸、聚丙烯酸、马来酸,β-羟基丁酸中的一种或多种。
优选地,所述步骤1)无机助剂与再生后催化剂上总金属组分的原子摩尔比为0.003:1~0.1:1;有机螯合配体助剂与催化剂上总金属组分的原子摩尔比为0.01:1~2:1。
进一步优选地,所述步骤1)无机助剂与再生后催化剂上总金属组分的原子摩尔比为0.01:1~0.05:1;有机螯合配体助剂与催化剂上总金属组分的原子摩尔比为0.05:1~0.5:1。
进一步优选地,所述步骤1)催化剂上总金属组分指烧碳再生后、活化前氧化态催化剂中的第Ⅷ族和ⅥB族金属组分含量之和。
优选地,所述步骤1)声场条件为:超声波功率按浸渍溶液的体积计算为0.1~30.0W/ml,工作频率为5kHZ~100kHZ,温度为15~50℃,处理时间为5~150min。
进一步优选地,所述步骤1)声场条件为:超声波功率按浸渍溶液的体积计算为0.5~18.0W/ml,工作频率为15kHZ~80kHZ,温度为20℃~40℃,处理时间为10~80min。
优选地,所述步骤1)浸渍的方式可以是饱和浸渍或者是过饱和浸渍,可一步浸渍,也可分步浸渍,分步浸渍时,每次浸渍后,需要进行干燥,然后再进行下一步的浸渍。
优选地,所述步骤3)浸渍后的样品分为两步热处理,第一步热处理条件如下:温度为50℃~150℃,时间为3~15小时;第二步热处理条件如下:温度为100℃~500℃,时间为1~200min。
优选地,所述步骤3)浸渍后的样品分为两步热处理,第一步热处理条件如下:温度为100℃~120℃,时间为5~12小时;第二步热处理条件如下:温度为150℃~280℃,时间为30~120min。
本发明具有以下有益效果:
(1)催化剂活化过程中使用适宜的超声波处理,超声空化作用能够增加再生后催化剂的有效表面积,增加反应的活性中心,产生更多的活性位。超声空化作用产生的冲击波和微射流能够使部分聚集的活性组分重新分散。超声场能够激活低活性金属,在硫化过程中形成更多的高活性反应中心,使再生后催化剂中金属活性增加。因此,本发明方法能够使再生后的催化剂产生更多的表面活性中心,提高反应活性,降低再生催化剂的生产成本。
(2)含有鳌合配体有机助剂的浸渍液,在浸渍过程中通过超声处理,利用超声波自身的催化作用能够加大有机助剂与再生催化剂中镍或钴的络合能力,有机助剂和Ni或Co之间的强相互作用使Ni或Co的硫化温度比Mo或W的硫化温度高,延迟Ni或Co的硫化,使钼或钨的硫化度增高,更加容易形成高活性的Ⅱ类Ni(Co)-Mo(W)-S活性中心,提高催化剂的活性。本发明所使用的鳌合配体有机助剂为环保型助剂,再生剂复活过程中没有氨氮化合物产生。
具体实施方式
下面通过实施例对本发明做进一步阐述,这是为了说明本发明,但本发明并不局限于下述实施例。
本发明的实施例是在采用50ml小型加氢反应装置中进行活性评价试验,所用原料性质见表1。催化剂在使用前要进行预硫化,硫化油为直馏煤油,其中加入质量分数为5%的DMDS(二甲基二硫),预硫化后直接引入原料油进行试验反应,预硫化及试验条件见表2。
表1原料油性质
原料油 | |
密度(20℃),g/cm<sup>3</sup> | 0.918 |
硫含量,wt% | 1.65 |
氮含量,μg/g | 1230 |
表2预硫化和试验条件
项目 | 预硫化条件 | 试验条件 |
压力,MPa | 5.5 | 5.5 |
温度,℃ | 325 | 343 |
LHSV,h<sup>-1</sup> | 1.0 | 1.0 |
氢油体积比 | 1000:1 | 1000:1 |
实施例1
称取一定量的烧炭后催化剂A1,用含有磷酸、酒石酸和丙三醇的水溶液,采用超声波浸渍法进行浸渍。浸渍液中磷、酒石酸和丙三醇与再生剂上总金属原子的摩尔比为0.02:0.08:0.06:1,超声波的功率为1:0W/ml,频率为45kHZ,温度为45℃,时间为25min,浸渍后样品室温晾干,第一步干燥温度为100℃,干燥时间8小时,第二步干燥温度为180℃,干燥时间30min,得到催化剂A-1。
实施例2
称取一定量的烧炭后催化剂A2,用含有磷酸、苹果酸和丙三醇的水溶液,采用超声波浸渍法进行浸渍。溶液中磷、苹果酸和丙三醇与再生剂上总金属原子的摩尔比为0.03:0.1:0.02:1,超声波的功率为15W/ml,频率为60kHZ,温度为:35℃,时间为30min,浸渍后样品室温晾干,第一步干燥温度为130℃,干燥时间6小时,第二步干燥温度为160℃,干燥时间75min,得到催化剂A-2。
实施例3
称取一定量的烧炭后催化剂A3,用含有磷酸、柠檬酸和丁二醇的水溶液,采用超声波浸渍法进行浸渍。溶液中磷和柠檬酸和丁二醇与再生剂上总金属原子的摩尔比为0.02:0.3:0.08:1,超声波的功率为15W/ml,频率为50kHZ,温度为:30℃,时间为30min,浸渍后样品室温晾干,第一步干燥温度为100℃,干燥时间10小时,第二步干燥温度为170℃,干燥时间100min,得到催化剂A-3。
实施例4
称取一定量的烧炭后催化剂A4,用含有羟基硅油、马来酸和三缩二乙二醇的水溶液,采用超声波浸渍法进行浸渍。溶液中硅和马来酸和三缩二乙二醇与再生剂上总金属原子的摩尔比为0.02:0.15:0.07:1,超声波的功率为20W/ml,频率为50kHZ,温度为:40℃,时间为45min,浸渍后样品室温晾干,第一步干燥温度为125℃,干燥时间6小时,第二步干燥温度为150℃,干燥时间60min,得到催化剂A-4。
实施例5
称取一定量的烧炭后催化剂A5,用含有羧基硅油、草酸和乙二醇的水溶液,采用超声波浸渍法进行浸渍。溶液中磷和草酸与再生剂上总金属原子的摩尔比为0.04:0.35:0.08:1,超声波的功率为18W/ml,频率为60kHZ,温度为:38℃,时间为55min,浸渍后样品室温晾干,第一步干燥温度为120℃,干燥时间8小时,第二步干燥温度为150℃,干燥时间60min,得到催化剂A-5。
对比例1
称取一定量的烧炭后催化剂A6,用含有磷酸、酒石酸的水溶液,采用常规浸渍法进行浸渍。溶液中磷和酒石酸与再生剂上总金属原子的摩尔比为0.04:1~0.35:1,浸渍后样品室温晾干,第一步干燥温度为120℃,干燥时间8小时,第二步干燥温度为150℃,干燥时间60min,得到催化剂A-6。
对比例2
称取一定量的再生催化剂A-7,直接进行活性评价。
对比例3
称取一定量的烧炭后催化剂A5,与实施例5不同的是水溶液中没有羧基硅油。得到催化剂A-8。
对比例4
称取一定量的烧炭后催化剂A5,与实施例5不同的是水溶液中没有草酸。得到催化剂A-9。
对比例5
称取一定量的烧炭后催化剂A5,与实施例5不同的是水溶液中没有乙二醇。得到催化剂A-10。
表3催化剂的初活性评价结果
A-1~A10再生后催化剂的初期活性评价结果见表3。由表3中数据可见,采用本发明方法制备的催化剂的活性明显高于对比例方法制备的催化剂。
表4催化剂1200h活性评价结果
A-1~A-10催化剂1200h活性评价结果见表4,由表4中数据可以看出,本发明方法制备的催化剂活性好,有利于长周期运转。
此外,需要说明的是,本说明书中所描述的以上内容仅仅是对本发明所作的举例说明。凡依据本发明专利构思所述的构造、特征及原理所做的等效变化或者简单变化,均包括于本发明专利的保护范围内。本发明所属技术领域的技术人员可以对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代,只要不偏离本发明的内容或者超越本权利要求书所定义的范围,均应属于本发明的保护范围。
Claims (10)
1.一种重质馏分油加氢处理催化剂再生复活方法,其特征在于:所述方法包括以下步骤:
1)再生后催化剂置于含无机助剂、有机螯合配体助剂的溶液中,在声场条件下进行浸渍;
2)浸渍后的样品室温晾干;
3)晾干后的样品经两步热处理得到活化的催化剂。
2.根据权利要求1所述的方法,其特征在于:所述步骤1)无机助剂为含有P、Si物质的一种或几种组合,其中含P的物质为磷酸,含Si的物质为羟基硅油或羧基硅油或其他。
3.根据权利要求1所述的方法,其特征在于:所述步骤1)有机螯合配体助剂为含羟基化合物或羧基化合物的或其组合。
4.根据权利要求3所述的方法,其特征在于:所述羟基化合物为丙三醇、丁二醇、山梨糖醇、聚乙二醇、聚丁烯醇、二乙二醇、三缩二乙二醇、乙二醇中的一种或多种的组合。
5.根据权利要求3所述的方法,其特征在于:所述羧酸类化合物为草酸、酒石酸、柠檬酸、苹果酸、水杨酸、D-葡萄糖、乳酸、聚丙烯酸、马来酸,β-羟基丁酸中的一种或多种。
6.根据权利要求3所述的方法,其特征在于:所述步骤1)无机助剂与再生后催化剂上总金属组分的原子摩尔比为(0.003~0.1):1;有机螯合配体助剂与催化剂上总金属组分的原子摩尔比为(0.01~2):1。
7.根据权利要求6所述的方法,其特征在于:所述步骤1)催化剂上总金属组分指烧碳再生后、活化前氧化态催化剂中的第Ⅷ族和ⅥB族金属组分含量之和。
8.根据权利要求3所述的方法,其特征在于:所述步骤1)声场条件为:超声波功率按浸渍溶液的体积计算为0.1~30.0W/ml,工作频率为5kHZ~100kHZ,温度为15~50℃,处理时间为5~150min。
9.根据权利要求3所述的方法,其特征在于:所述步骤1)浸渍的方式可以是饱和浸渍或者是过饱和浸渍,可一步浸渍,也可分步浸渍,分步浸渍时,每次浸渍后,需要进行干燥,然后再进行下一步的浸渍。
10.根据权利要求3所述的方法,其特征在于:所述步骤3)浸渍后的样品分为两步热处理,第一步热处理条件如下:温度为50℃~150℃,时间为3~15小时;第二步热处理条件如下:温度为100℃~500℃,时间为1~200min。
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