CN1237919A - 含磷催化剂及使用该催化剂进行石油加氢处理的方法 - Google Patents
含磷催化剂及使用该催化剂进行石油加氢处理的方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title description 13
- 229910052698 phosphorus Inorganic materials 0.000 title description 13
- 239000011574 phosphorus Substances 0.000 title description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000011148 porous material Substances 0.000 claims abstract description 22
- 238000001354 calcination Methods 0.000 claims description 14
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
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- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 239000011733 molybdenum Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 7
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- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 229910000428 cobalt oxide Inorganic materials 0.000 abstract description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 abstract description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 abstract description 3
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- 229910000476 molybdenum oxide Inorganic materials 0.000 abstract description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
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- 150000001868 cobalt Chemical class 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
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- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical group N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
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- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 1
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- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
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- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B01J35/615—100-500 m2/g
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- 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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Abstract
本发明涉及一种基于氧化铝的催化剂，按氧化物的重量含量表示，它含有：2%—10%(重量)的CoO，10%—30%(重量)的MoO3和4%—10%(重量)的P2O5，该催化剂的BET表面积是100—300m2/g，ESH压碎值大于1.4MPa，平均孔直径为8—11nm，直径大于14nm的孔的孔体积小于0.08ml/g，直径小于8nm的孔的孔体积至多等于0.05ml/g，直径为8—14nm孔的体积为0.20—0.8ml/g。本发明还涉及应用该催化剂的加氢处理方法，尤其是加氢脱硫。
Description
本发明涉及烃类石油进料的加氢处理催化剂，该催化剂含钴、钼和磷。
石油馏分的加氢处理在石油炼制工业中愈来愈重要，这一方面是因为对更重馏分进行转化的需求不断增长，另一方面是因为对终产品的特定性要求愈来愈严格。
这一现状是由最大限度地利用进口原油的经济利益导致的。而进口原油中重馏分的含量愈来愈高，这一方面表现为重馏分和由重馏分生产的较轻馏分相对贫氢，另一方面表现为重馏分中例如硫或氮的杂原子含量较高。
一般而言，加氢处理是对石油烃馏分的纯化处理，其中对馏分的碳原子骨架结构没有明显的改性。故此它包括：脱除例如硫或氮的杂原子；脱除金属；同时进行部分或全部的氢化。当这些操作是必需的时候，石油馏分被加氢处理，然后脱除形成的产品，从而可以收集到纯化的产品。
加氢处理“深度(profondeur)”与操作条件直接相关。所谓“操作条件”，必须理解为进料性质、反应区内总压、各种成分的分压、反应温度、每小时空速及氢气流率。一般说来，进料越重和/或越难于转化，其操作条件越苛刻，换言之，如果每小时空速保持恒定，则压力、温度和氢气流率必须提高。
申请人针对大量载体，用多种组成进行了研究，结果令人惊异地发现了一种催化剂，其加氢处理活性比之现有技术的催化剂优越许多。所述催化剂基于氧化铝，并按氧化物的重量含量表示，含有2％-10％的CoO,10％-30％的MoO3和4％-10％的P2O5，且该催化剂优选地具有颗粒状的理化特征。
所用的基质基于氧化铝(至少50％(重量)氧化铝)，优选基本由氧化铝构成。
该催化剂的特征在于，其中以五氧化二磷(P2O5)相对于最终催化剂的重量百分比表示的磷含量，为4.0％-10.0％，优选4.5％-8.0％，更优选5.6-8.0％，甚至更优选5.6-6.5％。该催化剂的特征在于，其中以氧化钴(CoO)相对于最终催化剂的重量百分比表示的钴含量，为2.0％-10.0％，优选3.5％-7.0％，更优选3.5％-5.5％。该催化剂的特征还在于，其中以氧化钼(MoO3)相对于最终催化剂的重量百分比表示的钼含量，为10％-30％，有利地为10.0％-18.9％，优选15.0-18.9％，更优选16.0-18.5％。
该催化剂表征如下：
BET表面积：对最终催化剂测量的BET表面积为100-300平方米/克，优选120-250平方米/克，更优选为130-240平方米/克。
ESH：Shell压碎值(l′écrasement Shell)，称作ESH。对最终催化剂测量，为大于1.4MPa，优选大于1.6MPa。
平均孔径：使用汞孔径仪得到孔分布，由此测得平均孔径。从孔分布曲线计算得到其微分曲线(la courbe dérivé)。微分曲线有一个或几个极大值，其纵坐标代表孔径。要求保护的催化剂为，这些极大值对应的孔径为80-110(10=1nm)，优选为95-110，甚至更优选为100-110。
小于80孔的孔体积：直径小于80的孔的孔体积至多等于0.05毫升/充，优选至多等于0.035毫升/克，甚至更优选至多等于0.025毫升/克。
大于140孔的孔体积：直径大于140的孔的孔体积为小于0.08毫升/克，优选小于0.06毫升/克，甚至更优选小于0.05毫升/克。几乎没有大于250的孔，更一般地，其孔体积小于总孔体积的10％，小于8％更好。
80-140孔的孔体积：直径为80-140的孔的孔体积为0.20-0.80毫升/克，优选为0.30-0.70毫升/克，且20％-60％的孔体积包含直径100-130的孔。
本发明的催化剂可按本领域技术人员已知的任何方法制备。
加氢元素可加入到混合物中或在成形后加入(优选方案)。
成形后继以煅烧，加氢元素在煅烧之前或之后加入。任何情况下，在250℃-600℃下煅烧后，制备结束。
本发明中一种优选的方法在于，将氧化铝的含水凝胶捏和几十分钟，使得到的糊状物通过一个漏斗形成直径优选为0.4-4毫米的挤出物。
该催化剂还具有加氢功能。加氢功能是由钼或钴提供的。它们可以在不同制备阶段以不同方式加入。
可以在捏和被选择作为基质的氧化物凝胶的时候仅仅部分加入或全部加入这些成分，剩余的加氢元素在捏和之后加入，更一般地是在煅烧后加入。
无论采用何种加入方式，优选地在加入钴的同时或加完钴之后再加入钼。
加氢元素的加入优选借助含这些金属的盐前体溶液，对被煅烧载体进行一次或几次离子交换操作完成。
如果氧化钼前体已经事先在捏和载体时加入，那么可以通过用一种或多种氧化钴前体溶液浸渍载体一次或多次，借此将其加入。
如果用相应的盐前体溶液浸渍一次或多次借以加入这些元素，则必须进行催化剂的中间煅烧步骤，煅烧温度为250-600℃。
可以在制备的任何阶段加入磷。它可单独加入，也可与钴和/或钼混合加入，例如可以在氧化铝胶溶化之前加入。它可以例如加入到挤出物形式的氧化铝中，辅以中间煅烧或不进行中间煅烧。它还可以与钴或钼全部或部分混合，加入到挤出物形式的氧化铝中，辅以中间煅烧或不进行中间煅烧。它也可以全部或部分地与钴或钼加入到挤出物形式的氧化铝中，辅以中间煅烧或不进行中间煅烧。它也可以最后单独加入。最后应当注意的是，这一列举仅供说明之用，因为还可以设想到许多变通方案。
金属元素以其氧化物的形式加入。为保证活性，它必须被硫化，应注意所有的就地硫化和异地硫化方法均可采用。
本发明还涉及使用该催化剂的加氢处理方法。
被处理进料是多种多样的，可以是从石脑油(起始沸点80℃)到真空蒸馏馏分，到真空蒸馏残余物。
总压为0.5-20MPa，温度为200-480℃，优选260-450℃，每小时空速为20-0.05h-1，而相对于每升进料的氢气流率是100-3,000升。氢气分压优选较低，为0.5-6MPa,0.5-5.5MPa更佳。在两种极限的情况下，对石脑油的加氢脱硫在1.5MPa压力、300℃、每小时空速10h-1和氢气流率100升/升进料的条件下进行；对脱除了沥青的真空蒸馏残余物的脱硫处理在20MPa压力、390℃、每小时空速O.5h-1和氢气流率为1500升/升进料的条件下进行。
下面的实施例说明本发明，而不对其范围构成限制。
大量制备了一种基于氧化铝的载体。为此，采用Condea公司销售的SB3凝胶。该凝胶与水和硝酸混合，然后捏和15分钟。捏和结束之后，所得的糊状物通过一圆柱形漏斗以制得直径为1.2毫米的挤出物。挤出物然后在120℃干燥过夜，在550℃煅烧2小时，煅烧气氛是含7.5％(体积)水的湿空气。实施例1：催化剂C1(不按照本发明)
向挤出的载体中加入钴、钼和磷。用浸渍载体至干的方式同时加入这三种元素的盐。所用钴盐是硝酸钴Co(NO3)2·6H2O，钼盐用七钼酸铵Mo7O24(NH4)6·4H2O，磷按H3PO4的形式加入。浸渍至干后，挤出物在120℃干燥过夜，然后在含7.5％(体积)水的湿空气中于550℃煅烧2小时。金属氧化物的最终含量及主要的理化特征如下：
MoO3(％(重量))： 18.2
CoO(％(重量))： 4.1
P2O5(％(重量))： 1.9
SBET(m2/g)： 205
ESH(MPa)： 1.3实施例2：催化剂C2(按照本发明)
向挤出的载体中加入钴、钼和磷。用浸渍至干的方法同时向挤出载体中加入这三种元素的盐。所用的钴盐是硝酸钴Co(NO3)2·6H2O。钼盐是七钼酸铵Mo7O24(NH4)6·4H2O，磷以H3PO4的形式加入。浸渍至干后，挤出物在120℃干燥过夜，然后在含7.5％(体积)水的空气中于550℃煅烧2小时。金属氧化物的最终含量及主要的理化特征如下：
MoO3(％(重量))： 18.2
CoO(％(重量))： 4.1
P2O5(％(重量))： 5.7
SBET(m2/g)： 170
ESH(MPa)： 1.8实施例3：催化剂C3(不按照本发明，对比)
向挤出载体中加入钴和钼。用浸渍至干的方法同时向载体中加入这三种元素的盐。所用的钴盐是硝酸钴Co(NO3)2·6H2O，所用钼盐是七钼酸铵Mo7O24(NH4)6·4H2O。浸渍至干后，挤出物在120℃干燥过夜，然后在含7.5％(体积)水的空气中于550℃煅烧2小时。金属氧化物的最终含量及主要的理化特征如下：
MoO3(％(重量))： 18.2
CoO(％(重量))： 4.1
P2O5(％(重量))： 0
SBET(m2/g)： 235
ESH(MPa)： 1.2实施例4：对比实验：甲苯加氢
对比了上述三种催化剂对甲苯加氢的活性。使用前对催化剂就地硫化。反应在3MPa、300℃下进行。进料为甲苯，其中加有2％(重量)的DMDS。其相对活性报告于下表。选择不含磷的催化剂C3作为对照。
催化剂 活性
C1 ： 126
C2 ： 152
C3 ： 100
可观察到含磷的两种催化剂活性高于不含磷催化剂。另外可观察到含高比例磷的催化剂比含少量磷的催化剂活性明显高得多。实施例5：对比试验：GDSR的HDS
对比了上述三种催化剂对真实进料的活性。使用前对催化剂进行就地硫化。测量了直接蒸馏汽油(GOSR)的加氢脱硫(HDS)活性。其主要的理化性质列于下表：
15℃的密度 ： 0.856
20℃的折射率 ： 1.4564
50℃的粘度 ： 3.72cSt=3.72×10-6m2/s
硫 ： 1.57％(重量)
模拟蒸馏：
起始产物： 153℃
5％： 222℃
50％： 315℃
95％： 415℃
终产物： 448℃
汽油的HDS试验在固定床内进行，其操作条件如下：
总压 ： 3MPa
每小时空速： 2h-1
温度 ： 310,340和360℃
氢气流率 ： 250升/升进料
三种反应温度下三种催化剂的催化性能列于下表。它表示为活性，以每一温度下不含磷催化剂C3的活性作为对比。
催化剂 310℃ 340℃ 360℃
C1 117 115 118
C2 123 128 129
C3 100 100 100
可见，本发明催化剂C2活性显著要高。
因此本发明的催化剂尤其适用于加氢脱硫。
Claims (8)
1．基于氧化铝的催化剂，按氧化物的重量含量表示，此催化剂含有：2-10％(重量)的CoO，10-30％(重量)的MoO3和4-10％(重量)的P2O5，其BET表面积为100-300m2/g，ESH压碎值大于1.4MPa，平均孔径为8-11nm，孔直径大于14nm的孔的孔体积小于0.08ml/g，孔直径小于8nm的孔的孔体积最多等于0.05ml/g，孔直径8-14nm的孔的孔体积为0.20-0.8ml/g。
2．上述权利要求的催化剂，其中P2O5含量为4.5％-8.0％。
3．上述权利要求中任一项的催化剂，其中P2O5的含量为5.6％-8.0％。
4．上述权利要求中任一项的催化剂，其中CoO的含量为3.5％-7.0％,MoO3含量为10.0％-18.9％。
5．上述权利要求中任一项的催化剂，按如下方法制备：用含钴、含钼溶液和磷酸溶液浸渍基于氧化铝的被煅烧基质，继以干燥和在湿空气中煅烧。
6．使用权利要求1-5中任一项的催化剂对石油进料进行加氢处理的方法，操作条件是：200-480℃、0.5-20MPa压力、每小时空速0.05-20h-1，氢气流率为100-3000升/升进料。
7．权利要求6的方法，其操作压力为0.5-6MPa。
8．权利要求6或7之一的方法，其中加氢处理是加氢脱硫。
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| Application Number | Priority Date | Filing Date | Title |
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| FR9613797A FR2755625B1 (fr) | 1996-11-13 | 1996-11-13 | Catalyseur contenant du phosphore et procede d'hydrotraitement de charges petrolieres avec ce catalyseur |
| FR96/13797 | 1996-11-13 |
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| CN1237919A true CN1237919A (zh) | 1999-12-08 |
| CN1108190C CN1108190C (zh) | 2003-05-14 |
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| CN97199666A Expired - Lifetime CN1108190C (zh) | 1996-11-13 | 1997-11-07 | 含磷催化剂及使用该催化剂进行石油加氢处理的方法 |
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| EP (1) | EP0952888B1 (zh) |
| JP (1) | JP2001503328A (zh) |
| KR (1) | KR100473668B1 (zh) |
| CN (1) | CN1108190C (zh) |
| AT (1) | ATE249276T1 (zh) |
| AU (1) | AU731209B2 (zh) |
| BR (1) | BR9713345A (zh) |
| CA (1) | CA2270590A1 (zh) |
| DE (1) | DE69724820T2 (zh) |
| DK (1) | DK0952888T3 (zh) |
| FR (1) | FR2755625B1 (zh) |
| NZ (1) | NZ335179A (zh) |
| RU (1) | RU2192923C2 (zh) |
| WO (1) | WO1998020969A1 (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101428214B (zh) * | 2007-11-07 | 2011-01-19 | 中国科学院大连化学物理研究所 | 氧化铝负载类贵金属催化剂在纤维素加氢水解中的应用 |
| CN101428213B (zh) * | 2007-11-07 | 2011-04-20 | 中国科学院大连化学物理研究所 | 炭载类贵金属催化剂在纤维素加氢水解反应中的应用 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2998488B1 (fr) * | 2012-11-29 | 2015-02-06 | Ifp Energies Now | Catalyseur d hydrotraitement a partir d alumine gel et methode de preparation d un tel catalyseur |
| FR3022156B1 (fr) * | 2014-06-13 | 2018-02-23 | Ifp Energies Now | Catalyseur mesoporeux et macroporeux a phase active comalaxee, son procede de preparation et son utilisation en hydrotraitement de residus |
| RU2616601C1 (ru) * | 2016-03-10 | 2017-04-18 | Открытое акционерное общество "Нефтяная компания "Роснефть" | Катализатор гидрооблагораживания вакуумного газойля и способы его приготовления (варианты) |
| RU2620267C1 (ru) * | 2016-03-17 | 2017-05-24 | Открытое акционерное общество "Нефтяная компания "Роснефть" | Катализатор гидрооблагораживания вакуумного газойля и способ его приготовления |
| US11788017B2 (en) | 2017-02-12 | 2023-10-17 | Magëmã Technology LLC | Multi-stage process and device for reducing environmental contaminants in heavy marine fuel oil |
| US12071592B2 (en) | 2017-02-12 | 2024-08-27 | Magēmā Technology LLC | Multi-stage process and device utilizing structured catalyst beds and reactive distillation for the production of a low sulfur heavy marine fuel oil |
| US10604709B2 (en) | 2017-02-12 | 2020-03-31 | Magēmā Technology LLC | Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials |
| US12025435B2 (en) | 2017-02-12 | 2024-07-02 | Magēmã Technology LLC | Multi-stage device and process for production of a low sulfur heavy marine fuel oil |
| US10655074B2 (en) | 2017-02-12 | 2020-05-19 | Mag{hacek over (e)}m{hacek over (a)} Technology LLC | Multi-stage process and device for reducing environmental contaminates in heavy marine fuel oil |
| RU2712446C1 (ru) * | 2019-07-30 | 2020-01-29 | Акционерное общество "Специальное конструкторско-технологическое бюро "Катализатор" | Способ приготовления носителя для катализаторов на основе оксида алюминия |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4752376A (en) * | 1985-09-25 | 1988-06-21 | Intevep, S.A. | Multiple stepped process for the demetallization and desulfuration of heavy oil feedstocks |
| US4941964A (en) * | 1988-03-14 | 1990-07-17 | Texaco Inc. | Hydrotreatment process employing catalyst with specified pore size distribution |
| JPH01270945A (ja) * | 1988-04-21 | 1989-10-30 | Sumitomo Metal Mining Co Ltd | 炭化水素の水素化処理用触媒 |
| US4940530A (en) * | 1989-02-21 | 1990-07-10 | Amoco Corporation | Two-stage hydrocarbon conversion process |
| SG66283A1 (en) * | 1990-08-03 | 1999-07-20 | Akzo Nobel Nv | Hydrotreating catalyst composition preparation and use thereof |
| EP0526988A3 (en) * | 1991-07-10 | 1993-03-31 | Texaco Development Corporation | Hydrotreatment process employing a mono-modal catalyst with specified pore size distribution |
| US5397456A (en) * | 1993-02-19 | 1995-03-14 | Texaco Inc. | Hydroconversion process employing catalyst with specified pore size distribution |
-
1996
- 1996-11-13 FR FR9613797A patent/FR2755625B1/fr not_active Expired - Lifetime
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- 1997-11-07 AT AT97913278T patent/ATE249276T1/de not_active IP Right Cessation
- 1997-11-07 EP EP97913278A patent/EP0952888B1/fr not_active Revoked
- 1997-11-07 WO PCT/FR1997/002006 patent/WO1998020969A1/fr not_active Application Discontinuation
- 1997-11-07 BR BR9713345-0A patent/BR9713345A/pt not_active Application Discontinuation
- 1997-11-07 CA CA002270590A patent/CA2270590A1/fr not_active Abandoned
- 1997-11-07 NZ NZ335179A patent/NZ335179A/xx unknown
- 1997-11-07 JP JP52223698A patent/JP2001503328A/ja not_active Ceased
- 1997-11-07 DK DK97913278T patent/DK0952888T3/da active
- 1997-11-07 RU RU99112181/04A patent/RU2192923C2/ru active
- 1997-11-07 DE DE69724820T patent/DE69724820T2/de not_active Revoked
- 1997-11-07 CN CN97199666A patent/CN1108190C/zh not_active Expired - Lifetime
- 1997-11-07 KR KR10-1999-7004126A patent/KR100473668B1/ko not_active IP Right Cessation
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101428214B (zh) * | 2007-11-07 | 2011-01-19 | 中国科学院大连化学物理研究所 | 氧化铝负载类贵金属催化剂在纤维素加氢水解中的应用 |
| CN101428213B (zh) * | 2007-11-07 | 2011-04-20 | 中国科学院大连化学物理研究所 | 炭载类贵金属催化剂在纤维素加氢水解反应中的应用 |
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| Publication number | Publication date |
|---|---|
| CA2270590A1 (fr) | 1998-05-22 |
| KR20000053177A (ko) | 2000-08-25 |
| KR100473668B1 (ko) | 2005-03-07 |
| EP0952888A1 (fr) | 1999-11-03 |
| WO1998020969A1 (fr) | 1998-05-22 |
| EP0952888B1 (fr) | 2003-09-10 |
| AU731209B2 (en) | 2001-03-29 |
| FR2755625B1 (fr) | 1998-12-11 |
| NZ335179A (en) | 2000-12-22 |
| CN1108190C (zh) | 2003-05-14 |
| RU2192923C2 (ru) | 2002-11-20 |
| DE69724820T2 (de) | 2004-04-08 |
| DE69724820D1 (de) | 2003-10-16 |
| BR9713345A (pt) | 2000-05-09 |
| ATE249276T1 (de) | 2003-09-15 |
| JP2001503328A (ja) | 2001-03-13 |
| DK0952888T3 (da) | 2004-01-05 |
| FR2755625A1 (fr) | 1998-05-15 |
| AU5058598A (en) | 1998-06-03 |
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