CN1050151C - Cataluyst for slag oil suspension bed hydrogen cracking - Google Patents
Cataluyst for slag oil suspension bed hydrogen cracking Download PDFInfo
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- CN1050151C CN1050151C CN97121791A CN97121791A CN1050151C CN 1050151 C CN1050151 C CN 1050151C CN 97121791 A CN97121791 A CN 97121791A CN 97121791 A CN97121791 A CN 97121791A CN 1050151 C CN1050151 C CN 1050151C
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- Prior art keywords
- nitrate
- oil
- hydrogenation
- mixed solution
- catalyst
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- 238000005336 cracking Methods 0.000 title claims abstract description 6
- 239000012053 oil suspension Substances 0.000 title claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title 1
- 229910052739 hydrogen Inorganic materials 0.000 title 1
- 239000001257 hydrogen Substances 0.000 title 1
- 239000002893 slag Substances 0.000 title 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003921 oil Substances 0.000 abstract description 14
- 239000003054 catalyst Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 abstract description 7
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000295 fuel oil Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 150000002823 nitrates Chemical class 0.000 abstract description 3
- 239000000725 suspension Substances 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000007865 diluting Methods 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000003245 coal Substances 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
- 238000004945 emulsification Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- -1 nitric acid Salt Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000010909 process residue Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
本发明提供了一种用于渣油悬浮床加氢裂化催化剂，它是由硝酸镍、硝酸锰、硝酸铁、硝酸钴四种硝酸盐溶液混合后加水稀释而成。在四种硝酸盐的混合溶液中各组分的重量百分比为：硝酸镍50～80%、硝酸锰10～30%、硝酸铁4～20%、硝酸钴0.5～5%。这种混合液加水后的水溶液的pH值不大于3。这种催化剂与其它类型的悬浮床加氢催化剂相比，突出的优点是原料价廉易得，成本大大降低，而加氢及裂化活性基本相当，使稠油渣油悬浮床加氢工艺的操作成本大大降低，这对于发展稠油加工，增加中间馏分油和轻质油收率，提高油品质量，增强装置操作灵活性，发展重油轻质化工艺，具有十分重要的现实意义和显著的经济效益。The invention provides a hydrogenation cracking catalyst for a suspended bed of residual oil, which is prepared by mixing four nitrate solutions of nickel nitrate, manganese nitrate, iron nitrate and cobalt nitrate and then diluting with water. The weight percent of each component in the mixed solution of four kinds of nitrates is: nickel nitrate 50-80%, manganese nitrate 10-30%, iron nitrate 4-20%, cobalt nitrate 0.5-5%. The pH value of the aqueous solution after adding water to the mixed solution is not greater than 3. Compared with other types of suspended bed hydrogenation catalysts, this catalyst has the outstanding advantages that the raw materials are cheap and easy to obtain, the cost is greatly reduced, and the hydrogenation and cracking activities are basically the same, so that the operation of the heavy oil residue suspension bed hydrogenation process The cost is greatly reduced, which has very important practical significance and significant economic benefits for the development of heavy oil processing, increasing the yield of middle distillate oil and light oil, improving the quality of oil products, enhancing the flexibility of device operation, and developing the process of lightening heavy oil. benefit.
Description
本发明属于石油加工工艺用的催化剂，特别适用于渣油悬浮床加氢裂化工艺。The invention belongs to a catalyst for petroleum processing technology, and is especially suitable for the hydrocracking technology of residual oil suspension bed.
近年来，我国和其它发达国家正在积极研究开发一种新的石油渣油加氢转化工艺--渣油悬浮床加氢裂化工艺，这种工艺技术是在高分散型的催化剂存在下，在高温和高压条件下裂化渣油，在较高的空速下，一次通过式操作的转化率可达到70～90％。目前这种工艺已开发了十多种类型，所采用的催化剂也各不相同，有天然矿物、有载金属煤粉、有油溶性金属、有褐煤细粉等，但已有的工艺过程存在一定的缺陷，如有的工艺过程反应压力很高，有的催化剂成本昂贵，有的渣油转化率不高、成本和操作费用却较高，在经济上没有竞争力。In recent years, my country and other developed countries are actively researching and developing a new petroleum residue hydroconversion process-residue suspended bed hydrocracking process. And cracking residual oil under high pressure conditions, at a higher space velocity, the conversion rate of one-pass operation can reach 70-90%. At present, more than ten types of this process have been developed, and the catalysts used are also different. There are natural minerals, metal-loaded coal powder, oil-soluble metals, and lignite fine powder, etc., but there are certain problems in the existing process. For example, some processes have high reaction pressure, some catalysts are expensive, some residues have low conversion rate, high cost and operating expenses, and are not economically competitive.
本发明的目的是要开发一种低成本的渣油悬浮床加氢裂化催化剂，同时还要保持渣油有较高的转化率。The purpose of the present invention is to develop a low-cost residual oil suspended bed hydrocracking catalyst while maintaining a relatively high conversion rate of the residual oil.
本发明的目的是这样实现的，它是由硝酸镍、硝酸锰、硝酸铁、硝酸钴的混合溶液加水稀释而成，在这四种硝酸盐的混合液中，各组分的比例是：硝酸镍50～80％、硝酸锰10～30％、硝酸铁4～20％、硝酸钴0.5～5％，上述比例是指重量百分比。上述四种硝酸盐的混合水溶液的PH值不大于3。The object of the present invention is achieved in that it is formed by adding water to the mixed solution of nickel nitrate, manganese nitrate, ferric nitrate, cobalt nitrate and dilutes, in the mixed solution of these four kinds of nitrates, the ratio of each component is: nitric acid 50-80% of nickel, 10-30% of manganese nitrate, 4-20% of iron nitrate, 0.5-5% of cobalt nitrate, and the above proportions refer to percentage by weight. The pH value of the mixed aqueous solution of the above four nitrates is not more than 3.
本发明所述渣油悬浮床加氢催化剂，采用硝酸镍、硝酸锰、硝酸铁和硝酸钴为主要成分，原料易得，获取方便，制成催化剂成本大大降低，加氢及裂化活性与其它类型的催化剂相当，使处理稠油、渣油的悬浮床加氢工艺的操作费用大大降低。The residual oil suspended bed hydrogenation catalyst of the present invention adopts nickel nitrate, manganese nitrate, iron nitrate and cobalt nitrate as the main components, the raw materials are easy to obtain, the acquisition is convenient, the cost of the catalyst is greatly reduced, and the hydrogenation and cracking activity is higher than that of other types. The catalyst is equivalent, which greatly reduces the operating cost of the suspension bed hydrogenation process for heavy oil and residual oil.
下面结合实施例来进一步说明本发明的组成。The composition of the present invention will be further described below in conjunction with the examples.
硝酸盐的获取可以采用下述方法，取金属镍、锰、铁、钴分别与硝酸反应，得到相应的硝酸盐，即硝酸镍、硝酸锰、硝酸铁、硝酸钴(也可采用其它方法获取硝酸盐)。分别取硝酸镍70克，硝酸锰15克，硝酸铁13克及硝酸钴2克互相混合，制成混合溶液，再加水稀释至PH值不大于3即成为渣油悬浮床加氢裂化的催化剂，然后加入到原料渣油中进行乳化和硫化，乳化后的含有催化剂的渣油就可作为悬浮床加氢裂化的原料。The acquisition of nitrate can adopt following method, get metal nickel, manganese, iron, cobalt to react with nitric acid respectively, obtain corresponding nitrate, i.e. nickel nitrate, manganese nitrate, ferric nitrate, cobalt nitrate (also can adopt other methods to obtain nitric acid Salt). Take 70 grams of nickel nitrate, 15 grams of manganese nitrate, 13 grams of iron nitrate and 2 grams of cobalt nitrate and mix with each other to make a mixed solution, then dilute with water until the pH value is not more than 3 to become a catalyst for residual oil suspended bed hydrocracking. Then it is added to the raw material residual oil for emulsification and sulfuration, and the emulsified residual oil containing catalyst can be used as the raw material for suspension bed hydrocracking.
将上述催化剂用于渣油悬浮床加氢裂化工艺，其操作成本大大降低，使该工艺具有很强的竞争力，这对于开发我国大量的稠油加工，增加中间馏分油和轻质油收率，提高油品质量，增强装置操作灵活性，发展重油加工工业，特别是发展重油轻质化工艺具有十分重要的现实意义和显著的经济效益。The above-mentioned catalyst is used in the hydrocracking process of the suspended bed of residual oil, and its operating cost is greatly reduced, which makes the process highly competitive. , improve the quality of oil products, enhance the flexibility of device operation, and develop the heavy oil processing industry, especially the development of heavy oil lightening technology has very important practical significance and significant economic benefits.
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Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97121791A CN1050151C (en) | 1997-12-23 | 1997-12-23 | Cataluyst for slag oil suspension bed hydrogen cracking |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97121791A CN1050151C (en) | 1997-12-23 | 1997-12-23 | Cataluyst for slag oil suspension bed hydrogen cracking |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1182777A CN1182777A (en) | 1998-05-27 |
| CN1050151C true CN1050151C (en) | 2000-03-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN97121791A Expired - Fee Related CN1050151C (en) | 1997-12-23 | 1997-12-23 | Cataluyst for slag oil suspension bed hydrogen cracking |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100383221C (en) * | 2004-07-06 | 2008-04-23 | 中科合成油技术有限公司 | Method for application of waste iron base catalyst in hydrocracking of Fischer-Tropsch synthesized heavy hydrocarbon |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042482A (en) * | 1989-11-07 | 1990-05-30 | 湖北省化学研究所 | The preparation method of cobalt-molybdenum-carbonoxide transformation catalyst |
| CN1009656B (en) * | 1986-07-09 | 1990-09-19 | 日东化学工业株式社 | Method for stabilizing xanthene gum aqueous solution |
| CN1045359A (en) * | 1990-03-17 | 1990-09-19 | 湖北省化学研究所 | The preparation method of iron-chromium-molybdenum system-carbonoxide transformation catalyst |
| CN1016626B (en) * | 1989-04-18 | 1992-05-13 | 弗朗茨普拉瑟尔铁路机械工业有限公司 | Travelling track tamping machine comprising transversely and vertically adjustable tamping units |
| US5672264A (en) * | 1994-10-07 | 1997-09-30 | Board Of Trustees Operating Michigan State University | Methods of using stable supergallery pillared clay compositions |
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1997
- 1997-12-23 CN CN97121791A patent/CN1050151C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1009656B (en) * | 1986-07-09 | 1990-09-19 | 日东化学工业株式社 | Method for stabilizing xanthene gum aqueous solution |
| CN1016626B (en) * | 1989-04-18 | 1992-05-13 | 弗朗茨普拉瑟尔铁路机械工业有限公司 | Travelling track tamping machine comprising transversely and vertically adjustable tamping units |
| CN1042482A (en) * | 1989-11-07 | 1990-05-30 | 湖北省化学研究所 | The preparation method of cobalt-molybdenum-carbonoxide transformation catalyst |
| CN1045359A (en) * | 1990-03-17 | 1990-09-19 | 湖北省化学研究所 | The preparation method of iron-chromium-molybdenum system-carbonoxide transformation catalyst |
| US5672264A (en) * | 1994-10-07 | 1997-09-30 | Board Of Trustees Operating Michigan State University | Methods of using stable supergallery pillared clay compositions |
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| Publication number | Publication date |
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| CN1182777A (en) | 1998-05-27 |
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