CN1227251A - A kind of preparation method of solid alkali used for oil product refining - Google Patents
A kind of preparation method of solid alkali used for oil product refining Download PDFInfo
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- CN1227251A CN1227251A CN 98111762 CN98111762A CN1227251A CN 1227251 A CN1227251 A CN 1227251A CN 98111762 CN98111762 CN 98111762 CN 98111762 A CN98111762 A CN 98111762A CN 1227251 A CN1227251 A CN 1227251A
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- alkaline earth
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- 239000003513 alkali Substances 0.000 title claims abstract description 65
- 239000007787 solid Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000007670 refining Methods 0.000 title abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 9
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 239000002585 base Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000010926 purge Methods 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- 230000008929 regeneration Effects 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims 3
- 238000001035 drying Methods 0.000 claims 2
- 239000012467 final product Substances 0.000 claims 2
- 238000007598 dipping method Methods 0.000 claims 1
- 230000002779 inactivation Effects 0.000 claims 1
- 230000001172 regenerating effect Effects 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 20
- 239000002699 waste material Substances 0.000 abstract description 11
- 238000004332 deodorization Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 239000003518 caustics Substances 0.000 abstract description 5
- 239000000376 reactant Substances 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 3
- 230000009849 deactivation Effects 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- -1 alkaline earth metal salt Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
一种用于油品精制的固体碱的制备方法，它主要通过改进油品精制的工艺中的所使用的反应剂，使得该固体碱碱洗效果好于苛性碱液预碱洗效果，同时可使脱臭装置催化剂寿命延长，并无废碱液产生。其特点主要将碱金属碱和碱土金属碱的混合物通过浸渍或反应的办法担载在特定的载体上，使其成为固体碱，该固体碱在失活后仍可通过特定的方法再生获得。A preparation method for solid alkali used in oil refining, which mainly improves the reactant used in the oil refining process, so that the solid alkali alkali cleaning effect is better than the caustic lye pre-alkali washing effect, and can be used at the same time The service life of the catalyst in the deodorization device is prolonged, and no waste lye is generated. Its characteristics are mainly to load the mixture of alkali metal alkali and alkaline earth metal alkali on a specific carrier by impregnation or reaction, so that it becomes a solid alkali, which can still be regenerated by a specific method after deactivation.
Description
本发明涉及一种用于油品精制的固体碱的制备方法，它主要是对炼油工业中油品精制工艺中所使用的反应剂进行了改进。它主要通过改进油品精制的工艺中的所使用的反应剂，使得该固体碱碱洗效果好于苛性碱液预碱洗效果，同时可使脱臭装置催化剂寿命延长，并无废碱液产生。其特点主要通过将碱金属碱和碱土金属碱的混合物担载在特定的载体上，使其成为固体碱，该固体碱在失活后仍可通过特定的方法再生获得。The invention relates to a preparation method of a solid alkali used for oil refining, which mainly improves the reactant used in the oil refining process in the oil refining industry. It mainly improves the reactants used in the oil refining process, so that the solid alkali washing effect is better than the caustic alkali pre-alkali washing effect, and at the same time, it can prolong the catalyst life of the deodorization device, and no waste alkali is produced. Its characteristics are mainly by loading the mixture of alkali metal alkali and alkaline earth metal alkali on a specific carrier to make it a solid base, which can still be regenerated by a specific method after deactivation.
在炼油工业中，碱洗是油品精制工艺中的一个重要环节，目的是除去硫化氢等酸性物质。由于碱洗过程使用苛性碱水溶液，导致有大量废碱液产生，给环保带来沉重负担。到目前为止，针对碱洗过程中产生大量废碱液，还没有有效的解决办法。特别在汽油精制过程中，一般来自催化裂化装置的稳定汽油先经过预碱洗再进脱臭精制装置，几十年来，汽油预碱洗这一环节一直被炼厂广泛采用。虽然对汽油预碱洗方式不断进行技术改造，引入电场的预碱洗(又称电精制)效果也有改观，但汽油预碱洗废碱液问题一直没有解决。据有关资料统计，对汽油脱臭工艺来说，脱臭精制前汽油进行预碱洗的碱浓度一般在10％左右，碱油比高的为1∶3，低的为1∶40，碱液平均每周更换一次。因此，从这些数据中可以计算出，对于100万吨/年的催化裂化汽油脱臭精制装置，仅用于汽油预碱洗的碱液量至少要达数千吨。如此大的碱耗不仅增加投资，更重要的是废碱液的排放对环境保护带来很大压力。目前世界各国对工业过程中的碱洗问题给予极大关注，并进行了各种研究。目前的研究趋势为：(1)在各种工业过程中，完全取消苛性碱液的使用；(2)充分提高碱使用效率或进行有效碱循环以降低碱用量；(3)在废碱液排放之前，进行化学处理。因此，针对汽油脱臭精制问题，若能取消汽油预碱洗过程或改变目前的碱洗方式，将可能完全根治这一过程所带来的废碱液问题。目前，虽然可以以氨洗代替碱洗，但废氨液的处理也相当困难，氨洗在我国应用并不广泛。固体碱洗是解决这一问题的良好办法，但适用的固体反应剂(即固体碱)，却一直是广大科研工作者和现场工作人员所一直探索和研究的。In the oil refining industry, alkali washing is an important link in the oil refining process, the purpose is to remove acidic substances such as hydrogen sulfide. Because caustic alkali aqueous solution is used in the alkali washing process, a large amount of waste alkali is produced, which brings a heavy burden to environmental protection. So far, there is no effective solution for producing a large amount of waste lye in the alkaline cleaning process. Especially in the gasoline refining process, generally the stable gasoline from the catalytic cracking unit is pre-alkali washed before entering the deodorization refining unit. For decades, the gasoline pre-alkali washing has been widely used by refineries. Although the way of gasoline pre-alkali washing has been continuously technologically improved, and the effect of introducing electric field pre-alkali washing (also known as electric refining) has also improved, the problem of gasoline pre-alkali washing waste lye has not been resolved. According to relevant data statistics, for the gasoline deodorization process, the alkali concentration of gasoline pre-alkali washing before deodorization and refining is generally about 10%, the high alkali-oil ratio is 1:3, and the low is 1:40. Change it once a week. Therefore, it can be calculated from these data that for a 1,000,000-ton/year catalytic cracking gasoline deodorization and refining unit, the amount of lye used only for gasoline pre-alkali washing must be at least thousands of tons. Such a large alkali consumption not only increases investment, but more importantly, the discharge of waste alkali solution brings great pressure on environmental protection. At present, countries all over the world have paid great attention to the problem of alkali washing in industrial processes, and have carried out various researches. The current research trend is: (1) in various industrial processes, completely cancel the use of caustic lye; (2) fully improve the efficiency of alkali use or carry out effective alkali circulation to reduce the amount of alkali; (3) in the waste lye discharge Prior to chemical treatment. Therefore, for the problem of gasoline deodorization and refining, if the pre-alkali washing process of gasoline can be canceled or the current alkali washing method can be changed, it will be possible to completely eliminate the problem of waste lye caused by this process. At present, although ammonia washing can be used instead of alkali washing, the treatment of waste ammonia is also quite difficult, and ammonia washing is not widely used in my country. Solid alkali cleaning is a good way to solve this problem, but the applicable solid reactant (i.e. solid alkali) has always been explored and studied by numerous scientific research workers and field workers.
本发明的目的就在于避免现有技术中的不足之处而提供一种用于油品精制的固体碱的制备方法，它可代替液体碱，并根除废碱液的排放，同时使工艺达到精制油品的要求。它主要是将碱金属碱和碱土金属碱通过浸渍或反应的方法加载于特定的载体上而得到，其主要的技术特点是：对于易溶性的碱金属碱，是将碱的混合物溶于水中，按要求配成所需要浓度，并将载体在溶液中浸泡，当载体上的碱浓度达到要求时，干燥载体即可；对于难溶性的碱土金属碱，是先将易溶性的碱金属碱按前述方法担载于载体上，然后再与碱土金属盐进行反应，使之在载体上生成难溶性的碱土金属碱，然后干燥即可。对用于油品精制失活后的该固体碱，可用季铵盐类进行洗涤，然后再通过高温水蒸汽吹扫再生，即可得到再生后的固体碱。The purpose of the present invention is to avoid the deficiencies in the prior art and provide a method for preparing solid alkali for oil refining, which can replace liquid alkali, and eradicate the discharge of waste alkali liquor, while enabling the process to achieve refined oil requirements. It is mainly obtained by loading alkali metal alkali and alkaline earth metal alkali on a specific carrier by impregnation or reaction. Its main technical characteristics are: for easily soluble alkali metal alkali, the mixture of alkali is dissolved in water, Make the required concentration according to the requirements, and soak the carrier in the solution. When the alkali concentration on the carrier reaches the requirement, dry the carrier; The method loads it on the carrier, and then reacts with the alkaline earth metal salt to make it generate insoluble alkaline earth metal alkali on the carrier, and then it just needs to be dried. The solid base used for oil refining and deactivation can be washed with quaternary ammonium salts, and then regenerated by purging with high-temperature steam to obtain the regenerated solid base.
下面将结合实施例来详叙本发明的技术特点。The technical characteristics of the present invention will be described in detail below in conjunction with the embodiments.
在实际制备过程中，发明者所说的固体碱是以通过浸渍法或化学反应制得的担载型碱，所用的载体采用的是分子筛、硅胶、活性炭、三氧化铝、低铝和高铝硅酸盐等，所用的碱包括碱金属碱，如氢氧化钾、氢氧化钠；碱土金属碱，如氢氧化钙、氢氧化镁、氢氧化钡或它们的氧化物，如氧化钙、氧化镁、氧化钡；其它碱如氢氧化铵、氢氧化锌、氢氧化镍；或它们的混合物。In the actual preparation process, the solid base mentioned by the inventor is a supported base prepared by impregnation or chemical reaction, and the carrier used is molecular sieve, silica gel, activated carbon, alumina, low aluminum and high aluminum Silicate, etc., the alkali used includes alkali metal alkali, such as potassium hydroxide, sodium hydroxide; alkaline earth metal alkali, such as calcium hydroxide, magnesium hydroxide, barium hydroxide or their oxides, such as calcium oxide, magnesium oxide , barium oxide; other bases such as ammonium hydroxide, zinc hydroxide, nickel hydroxide; or mixtures thereof.
其固体碱的制备方法是：对于水溶性碱，先将一种碱或几种碱的混合物溶于水，按需要配成一定浓度的溶液，碱浓度通常在1％(重量)到40％(重量)之间。再以该碱液浸泡上述载体8到24小时(视设计要求而定)，退出多余碱液，干燥载体即可；对于难溶性碱，例如氢氧化镁，可以先将水溶性碱如氢氧化钠通过前述的办法担载于载体上，然后再与镁盐如氯化镁等反应，使之在载体上生成氢氧化镁，然后干燥即可。The preparation method of its solid base is: for water-soluble base, first a kind of base or the mixture of several bases is dissolved in water, and the solution of certain concentration is made into as required, and base concentration is usually in 1% (weight) to 40% ( weight). Soak the above-mentioned carrier with the lye for 8 to 24 hours (depending on the design requirements), withdraw the excess lye, and dry the carrier; for insoluble alkalis, such as magnesium hydroxide, water-soluble alkalis such as sodium hydroxide Carry it on the carrier by the aforementioned method, and then react with magnesium salt such as magnesium chloride to generate magnesium hydroxide on the carrier, and then dry it.
对失活后的固体碱的再生方法是，先以季铵盐类的汽油活化剂(如氯化十八烷基二甲基苄基铵)洗涤床层，再用高温水蒸气吹扫，即可使固体碱活性再生。The regeneration method to the deactivated solid base is to wash the bed layer with a gasoline activator (such as octadecyldimethylbenzyl ammonium chloride) of quaternary ammonium salts, and then use high-temperature steam to purge, i.e. Active regeneration of solid base can be achieved.
用上述方法制备出的固体碱，可用于炼油厂的油品精制设备来除去硫化氢及其它酸性物质，同时对炼厂其它过程也同样适用。固体碱预碱洗效果好于苛性碱液预碱洗效果，同时可使脱臭装置催化剂寿命延长。固体碱洗无废碱液产生，对环保有利并降低预碱洗费用，具有明显的社会效益。The solid alkali prepared by the above method can be used in the oil refining equipment of the refinery to remove hydrogen sulfide and other acidic substances, and it is also applicable to other processes of the refinery. The pre-alkali washing effect of solid alkali is better than that of caustic lye, and it can prolong the catalyst life of the deodorization device. Solid alkali washing does not produce waste alkali, which is beneficial to environmental protection and reduces the cost of pre-alkali washing, which has obvious social benefits.
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Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98111762A CN1102635C (en) | 1998-12-28 | 1998-12-28 | Method for preparing solid alkali for oil refinery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98111762A CN1102635C (en) | 1998-12-28 | 1998-12-28 | Method for preparing solid alkali for oil refinery |
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| CN1227251A true CN1227251A (en) | 1999-09-01 |
| CN1102635C CN1102635C (en) | 2003-03-05 |
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| CN98111762A Expired - Fee Related CN1102635C (en) | 1998-12-28 | 1998-12-28 | Method for preparing solid alkali for oil refinery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1317357C (en) * | 2005-01-27 | 2007-05-23 | 清华大学 | Solid alkali catalyst, preparation and use thereof |
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| CN101148602B (en) * | 2007-09-10 | 2011-01-12 | 蒋玉珊 | Alkaline purifying agent |
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| GB2281305A (en) * | 1993-08-27 | 1995-03-01 | John Robson Metals Limited | Removing chlorinated organic compounds from oil |
| CN1053213C (en) * | 1995-03-22 | 2000-06-07 | 中国石化茂名石油化工公司研究院 | Process for petroleum solvent refining of fine chemical products |
| CN1193041A (en) * | 1997-03-12 | 1998-09-16 | 抚顺市高新技术开发服务部 | Method for series absorption of refined oil products by absorbent |
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