CN106554802B - 一种油品脱氯剂的制备和使用方法 - Google Patents
一种油品脱氯剂的制备和使用方法 Download PDFInfo
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Classifications
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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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/02—Non-metals
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- 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
- 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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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
本发明涉及一种油品脱氯剂制备和使用方法。首先将活性炭加入强氧化性介质进行氧化改性得到改性活性炭,随后用可溶性金属盐和其他助剂的混合溶液进行负载处理,最后将负载后的改性活性炭在保护气氛或真空中干燥、活化后得到脱氯剂成品。本发明脱氯剂具有良好的选择吸附性和稳定性,脱氯效果好,在温和的条件下,可将油品中的有机氯化物降低至0.2ppm。
Description
技术领域
本发明属于石油化工领域,具体涉及一种油品脱氯剂及其制备和使用方法。
技术背景
近年来,世界许多油田开采已处于中后期,原油性质及开采条件恶化,为保持原油产量,各种采油助剂被广泛使用,其中不少采油助剂中含有有机氯化物,例如:含三氯乙烷等氯代烃的清蜡剂、甲基氯硅烷堵水剂、盐酸‐氟化氨酸化剂、季铵‐氯化铵复合稳定粘土剂等。这些有机氯化物不溶于水、热稳定性好,很难用电脱盐的方法脱除。有机氯化物的存在会对原油后续加工精制造成严重影响,例如,在重整加工过程中,原料经预加氢处理,有机氯化物将转化为氯化氢,氯化氢与水和氨分别形成盐酸和氯化铵,将会对设备造成严重的腐蚀并堵塞管道,严重时将导致装置被迫停工检修,给企业造成巨大的经济损失。近年来,不少炼油厂(如济南炼油厂)相继出现因氯含量超标而导致一些生产装置特别是重整装置设备腐蚀、管道堵塞、催化剂中毒等事件,大大降低了设备使用寿命,给生产带来一定危害,这已引起了生产厂家及科研人员越来越多的关注,并在这方面开展了大量的研究工作,取得了许多有关氯脱除的宝贵经验。
目前脱除有机氯的方法主要有催化加氢、电化学脱氯和生物脱氯,其中后两种方法主要针对水中有机氯化物的脱除。催化加氢是指在催化剂表面有机氯化物和氢反应生产氯化氢和相应的烃类,再用固体碱性氧化物吸收氯化氢的方法。此类脱氯剂有较多专利文献报道,如CN1800310A、CN1095388等。虽然催化加氢的方法可以彻底脱除有机氯化物,但其成本较高,且副反应多。有文献报道采用碱性物质和盐加入水中形成含氢氧根的溶液,然后与油品进行加热回流,最后再进行分离。这虽然能有效降低油品中的氯含量,但不可避免的会给油品中带入了一定量的水分,影响油品质量。总之,目前市售的油品脱(有机)氯剂大多存在制备工艺复杂、操作条件苛刻、适用范围窄、后续处理繁琐等缺陷。因此,开发一种新型高效脱(有机)氯剂是当前油品脱氯领域的当务之急。
发明内容
本发明的目的在于针对现有技术的不足,提供一种制备工艺简单、成本低、适用范围广、氯容量高、脱氯效果好的油品脱氯剂,该脱氯剂可在较为温和的条件下,脱除油品中绝大部分的有机氯。
本发明的另一目的在于提供一种使用本发明脱氯剂脱除油品中有机氯的方法。
为实现上述目的,本发明通过以下技术方案来实现:一种新型高效油品脱氯剂,包括以下制备步骤:
(1)将活性炭加入强氧化性介质中,在30~80℃下搅拌回流6~24h,干燥制得改性活性炭;
所述的活性炭为微孔活性炭,微孔孔径为0.2~50nm,优选0.2~10nm;
所述的强氧化性介质是浓度为5~30%的硝酸或5~30%双氧水;
(2)将改性活性炭置于杂多酸、硝酸镧和可溶性主族或过渡金属盐的混合溶液中浸渍6~24h制得负载的改性活性炭,其中改性活性炭:杂多酸:硝酸镧:可溶性主族或过渡金属盐=1:0.05~0.2:0.05~0.1:0.5~1.5(质量比);
所述的杂多酸为钼磷酸、钨磷酸、钨硅酸或钼硅酸中的一种或几种的混合物;
所述的可溶性主族或过渡金属盐为可溶性铝、镍、铁、锌、钴或铜盐的一种或几种的混合物;
(3)在氮气气氛、110℃条件下干燥4h,再200~400℃下活化1~4h制得本发明油品脱氯剂。
进一步的,一种新型高效油品脱氯剂的使用方法,包括以下步骤:
(1)按油品脱氯剂:油品=1:0.5~30的质量比向反应装置内加入脱氯剂和油品,搅拌并通入惰性气体排除反应器内氧气后,控制压力为0.1~2MPa,随后密闭反应器;
(2)控制反应装置内温度在25~200℃,并持续搅拌0.5~12h;
(3)停止加热,待冷却后过滤除脱氯剂即得脱除有机氯的油品。
进一步的,所述的油品为石脑油、汽油、柴油、煤油、裂解用石蜡油、润滑油、加氢原料油或液化石油气。
本发明脱氯剂具有以下优点:首先,活性炭具有很大的比表面积,对气体、溶液中的无机或有机物质都具有良好的吸附能力,氧化改性不但增加了活性炭微孔比例,也使其表面产生了大量羧基、内酯、酸酐、酚基等极性基团,进一步提高了活性炭对油品中的有机氯分子的吸附效率;其次,金属氧化物可与有机氯化物发生化学反应,生成相应的盐酸盐和烃类,是实现脱氯的关键。将金属氧化物均匀的负载到改性活性炭表面,不仅可增加金属氧化物表面积,而且可利用表面效应增大金属氧化物的反应活性。改性活性炭主要是物理吸附油品中有机氯化物,吸附脱附速率快,负载金属氧化物后,被吸附的有机氯化物可迅速转移到金属氧化物表面进行化学反应,二者具有协同作用;再次,杂多酸和镧元素的加入,可进一步增强有机氯等卤代烃在催化剂表面上的吸附,并对金属氧化物的脱氯反应起到催化作用,提高了其脱氯效率。因此,相比市售脱氯剂,本发明脱氯剂脱有机氯或卤化物效果尤其突出;最后,制备本发明脱氯剂的原料易得、价格低廉、合成工艺相对简单、使用条件温和,具有良好的应用前景。
具体实施方式
如下的实施例将更详细地描述本发明,但本发明不仅仅局限于这些具体的实施例中。
实施例1(改性活性炭的制备)
按照表1中A-G中的制备条件制备改性活性炭,步骤如下:在带有回流、搅拌装置的反应器内加入活性炭及强氧化介质,一定温度下搅拌若干小时,再经水洗、干燥后得到改性活性炭。
表1
实施例2(脱氯剂的制备)
将实施例1中制备的改性活性炭A-G置于用各种不同杂多酸、硝酸镧和可溶性主族或过渡金属盐配制的混合溶液中浸渍,再经干燥、活化后得到不同的脱氯剂产品。所用改性活性炭种类及用量、杂多酸种类及用量、硝酸盐种类及用量、浸渍时间、活化温度、活化时间如表2所示。
表2
实施例3(产品效果评价)
脱氯效果评价步骤如下:(1)向反应装置内加入实施例2制备的脱氯剂和某炼厂的石脑油(氯含量为51.4ppm),搅拌并通入惰性气体排除反应器内氧气后,控制压力为1.0MPa,随后密闭反应器,脱氯剂与油品的质量比为1:15;(2)控制反应装置内温度为150℃,并持续搅拌6h;(3)停止加热,冷却后取样分析氯含量,数据见表3。
表3
注:JX‐5D为一种市售脱氯剂
由表中数据可知,本发明脱氯剂Ⅱ、Ⅲ、Ⅶ、Ⅸ可将油品中的有机氯含量降低至1.0ppm以下,从脱氯效果上要明显优于市售脱氯剂JX‐5D。
Claims (3)
1.一种油品脱氯剂的制备方法,其特征在于,包括以下制备步骤:
(1)将活性炭加入强氧化性介质中,在30~80℃下搅拌回流6~24h后,用水洗涤至pH=5~7,再干燥而制得改性活性炭;
所述的活性炭为微孔活性炭,微孔孔径为0.2~50nm;
所述的强氧化性介质是质量百分浓度为5~30%的硝酸或5~30%双氧水;
(2)将改性活性炭置于杂多酸、硝酸镧和可溶性主族或过渡金属盐的混合溶液中浸渍6~24h制得负载的改性活性炭,各试剂质量比为改性活性炭:杂多酸:硝酸镧:可溶性主族或过渡金属盐=1:0.05~0.2:0.05~0.1:0.5~1.5;
所述的杂多酸为钼磷酸、钨磷酸、钨硅酸或钼硅酸中的一种或几种的混合物;
所述的可溶性主族或过渡金属盐为可溶性铝、镍、铁、锌、钴或铜盐的一种或几种的混合物;
(3)将负载的改性活性炭在氮气气氛、110℃条件下干燥4h,再200~400℃下活化1~4h制得油品脱氯剂。
2.一种油品脱氯剂的使用方法,其特征在于,包括以下步骤:
(1)向反应装置内按1:0.5~30的质量比加入采用权利要求1所述的制备方法制备的油品脱氯剂和油品,搅拌并通入惰性气体排除反应器内氧气后,控制压力为0.1~2MPa,随后密闭反应器;
(2)控制反应装置内温度在25~200℃,并持续搅拌0.5~12h;
(3)停止加热,待冷却后过滤除脱氯剂即得脱除有机氯的油品。
3.根据权利要求2所述的油品脱氯剂的使用方法,其特征在于,步骤(1)中所述油品为石脑油、汽油、柴油、煤油、裂解用石蜡油、润滑油、加氢原料油或液化石油气。
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