CN111617789A - 一种煤焦油加氢预处理催化剂及其制备方法 - Google Patents
一种煤焦油加氢预处理催化剂及其制备方法 Download PDFInfo
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 42
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 26
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- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
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Classifications
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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
- B01J27/19—Molybdenum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- 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
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- 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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- C—CHEMISTRY; METALLURGY
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- 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
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- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, or compounds thereof
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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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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Abstract
本发明公开了一种煤焦油加氢预处理催化剂及其制备方法。所述催化剂的孔容为0.9~1.5mL/g,比表面积200~300m2/g,最可几孔径为15~30nm,20~30nm以上大孔的孔体积占总孔容的45~70%。以氧化铝为载体,以VIB和VIII金属元素为活性组分,以磷元素为助剂,加氢预处理催化剂中活性组分以金属计的重量含量为0.4%~10%,助剂磷以元素计的重量含量为0.1%~10%。本发明提供的煤焦油加氢预处理催化剂具有大孔容大孔径,扩散性能优异,具有较高的脱金属和氢解沥青质活性。
Description
技术领域
本发明涉及一种加氢预处理催化剂及其制备方法,更具体地说是一种大孔径大孔容的煤焦油加氢预处理催化剂及其制备方法。
背景技术
煤焦油是煤在热解和气化过程中获得的一种宝贵化工原料。随着低阶煤热解技术的迅速发展,中低温煤焦油产量的大幅提升。中低温煤焦油含有较多的烷烃、环烷烃和较少的稠环芳烃,适宜通过加氢的方式生产清洁燃料油和高附加值化学品,
渣油属于石油基重油中最难加工的原料,含有大量胶质和沥青质,这部分物质分子量大、结构复杂,扩散困难,因此要求催化剂具有优良的孔道结构。与渣油相比较,煤焦油中所含的沥青质远大于渣油中的含量,由于沥青质分子直径大,含有大量杂原子和金属,在加氢过程中易于缩聚形成焦炭和发生金属沉积,堵塞催化剂孔道使其失活,从而对煤焦油加氢催化剂提出更高的要求。
煤焦油加氢预处理催化剂的孔结构是催化剂十分重要的性质。煤焦油中的沥青质分子及金属杂原子化合物直径都较大,煤焦油加氢属于扩散控制过程,需要催化剂具有较大的孔径以使重质组分大分子能够进入催化剂孔道,进而与催化剂表面活性位作用,同时需要大孔容容纳脱除的金属杂质,因此催化剂的孔结构对催化剂的反应效果有很大影响。
CN107303484A公开了一种含硅大孔氧化铝载体的制备方法,利用多元醇和/或糖类物质的水溶液浸渍拟薄水铝石并进行水热处理,加入用含硅溶液浸渍的炭黑粉,与助挤剂、胶溶剂混捏,制得含硅的氧化铝载体。使用炭黑粉作为扩孔剂添加量需在10%以上才会有效果,而且制得的载体强度较低。
CN104646005A公开了一种重油脱金属催化剂制备方法,称取拟薄水铝石,加入胶溶剂、助挤剂和扩孔剂,混捏、干燥、焙烧后喷淋酸性溶液,干燥后制得一种氧化铝载体,其孔容为0.71~0.85,平均孔直径19~30nm。
CN102847541A公开了一种煤焦油加氢脱金属催化剂及其制备方法,该方法将氧化铝载体先用有机酸溶液处理,再用硝酸铝溶液浸渍,经过干燥、焙烧得到改性氧化铝载体,然后将活性组分负载在载体上制得。该方法在载体改性过程步骤繁琐,且会产生二次污染。
上述方法所制备催化剂的孔容多在0.9mL/g以下,20~30nm以上大孔的孔体积占总孔容低于45%,不能避免较小的孔道发生孔口堵塞,不能最大程度改善催化剂的扩散性能。
发明内容
针对现有技术的不足,本发明提供一种新的大孔结构的煤焦油加氢预处理催化剂及其制备方法。本发明方法制备的催化剂20~30nm以上大孔的孔体积占总孔容的45~70%,扩散性能好,有效解决煤焦油中大量沥青质大分子物质向催化剂内部扩散和加氢转化的问题。本方法制备的催化剂孔容更大,可以容纳更多的金属和积炭,延长加氢装置开工周期。本发明制备过程简单、仅添加少量复合扩孔剂,焙烧过程能耗低、产品强度满足工业应用需求。本发明制备的催化剂可作为加氢保护剂、加氢脱金属剂和沥青质转化催化剂载体使用。
本发明提供一种煤焦油加氢预处理催化剂,其中,
孔容为0.9~1.5mL/g;
比表面积为200~300m2/g;
最可几孔径为15~30nm;
20~30nm以上大孔的孔体积占总孔容的45~70%。
以氧化铝为载体,以VIB和VIII金属元素为活性组分,加氢预处理催化剂中活性组分以金属计的重量含量为0.4%~10%。
以磷元素为助剂,助剂磷以元素计的重量含量为0.1%~10%。
本发明同时提供一种煤焦油加氢预处理催化剂的制备方法,包括如下步骤:
(1)采用滴定法制备出铝水化合物,在搅拌条件下加入含磷化合物,然后静置、冷却、洗涤、干燥得到含磷拟薄水铝石M。
(2)将含磷拟薄水铝石M与复合扩孔剂和助挤剂混合并成型、干燥、焙烧制得氧化铝载体;
(3)配制含有钼和/或钨,和镍和/或钴的金属溶液,并对(2)中所得载体以饱和浸渍的方式负载金属;物料洗涤、在50~120℃下干燥2~4小时,然后在400~700℃下焙烧2~6小时,催化剂中含有占催化剂总重量0.4%~10%的活性金属,磷元素含量占催化剂总重量的0.1%~10%。
本发明所述的煤焦油加氢预处理催化剂的制备方法,其中,所述的含磷拟薄水铝石M孔容为1.1~2.2mL/g,比表面积为130~500m2/g,最可几孔径为15~35nm。
本发明所述的煤焦油加氢预处理催化剂的制备方法,其中,所述的复合扩孔剂为含硼化合物和聚氧乙烯醚。
本发明所述的煤焦油加氢预处理催化剂的制备方法,其中,所述的聚氧乙烯醚为烷基酚聚氧乙烯醚、蓖麻油聚氧乙烯醚、脂肪胺聚氧乙烯醚、脂肪酸聚氧乙烯醚其中的一种或几种
本发明所述的煤焦油加氢预处理催化剂的制备方法,其中,所述的含硼化合物优选硼酸、氧化硼和硼酸盐中的一种或几种。
本发明所述的煤焦油加氢预处理催化剂的制备方法,其中,以硼计,所述的含硼化合物的加入量优选为拟薄水铝石干胶粉中对应的氧化铝重量的0.5~5%。
本发明所述的煤焦油加氢预处理催化剂的制备方法,其中,所述的聚氧乙烯醚的加入量优选为拟薄水铝石干胶粉中对应的氧化铝重量的0.5~3%。
本发明所述的煤焦油加氢预处理催化剂的制备方法,其中,所述的助挤剂优选为田菁粉或淀粉。
本发明所述的煤焦油加氢预处理催化剂的制备方法,其中,所述的助挤剂的加入量优选为拟薄水铝石干胶粉中对应的氧化铝重量的1~3%。
本发明煤焦油加氢预处理催化剂的形状可以根据不同的要求进行改变。
与现有技术相比,本发明提供的催化剂20~30nm以上大孔的孔体积占总孔容的45~70%,扩散性能更好,有效解决煤焦油中大量沥青质大分子物质向催化剂内部扩散和加氢转化的问题;本方法制备的催化剂孔容更大,可以容纳更多的金属和积炭,延长加氢装置开工周期;本发明提供的方法在制备过程中无需添加酸性胶溶剂,降低了酸对水合氧化铝粒子结构的破坏,有效保护氧化铝载体的孔道结构,使上大孔结构尽可能得以保存;本发明提供的拟薄水铝石胶溶性能好,在载体制备过程中无需添加粘结剂,大幅降低焙烧能耗并提高产品强度;使用含硼化合物与聚氧乙烯醚复合扩孔比两者单独使用,所得孔径孔容更大,同时扩孔剂加入量低,降低生产成本并提高载体强度。
本发明提供的煤焦油加氢预处理催化剂可做为固定床加氢催化剂煤焦油加氢预处理催化剂使用,特别是作为煤焦油加氢预处理催化剂制备重油加工用的加氢保护剂、脱金属催化剂和脱沥青质催化剂等加氢催化剂。
具体实施方式
以下对本发明的实施例作详细说明:本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和过程,但本发明的保护范围不限于下述实施例,下列实施例中未注明具体条件的实验方法,通常按照常规条件。
实施例1
制备含磷拟薄水铝石M,M中含有占其总重量1.04%的P。用氮气吸附法测定含磷拟薄水铝石M的比表面积和孔体积,M的比表面积为245m2/g,孔体积1.4mL/g,最可几孔径为20.8nm。
称取上述拟薄水铝石M100g(干基),加入田菁粉3g,将1.2g硼酸和0.6g聚氧乙烯醚溶解于110g去离子水中,加入前述物料中,混捏后在单螺杆挤条机上挤成直径2.5mm的圆柱形,105℃干燥4小时,再800℃焙烧4小时,得到氧化铝载体。配制含有(6.2gMoO3+4.8gNiO)/100mL的金属浸渍液,以饱和浸渍的方法对所得载体进行浸渍,在100℃下干燥4h,在550℃下焙烧4h,制得催化剂A,催化剂物性见表1。
实施例2
制备含磷拟薄水铝石M,M中含有占其总重量0.89%的P。用氮气吸附法测定含磷拟薄水铝石M的比表面积和孔体积,M的比表面积为224m2/g,孔体积1.5mL/g,最可几孔径为19.6nm。
称取上述拟薄水铝石M100g(干基),加入田菁粉3g和1.0g氧化硼,将1.7g聚氧乙烯醚溶解于107g去离子水中,加入前述物料中,混捏后在单螺杆挤条机上挤成直径3.0mm的三叶草形,120℃干燥3小时,再600℃焙烧5小时,得到氧化铝载体,配制含有(8.3gWO3+3.6gNiO)/100mL的金属浸渍液,以饱和浸渍的方法对所得载体进行浸渍,在105℃下干燥4h,在600℃下焙烧4h,制得催化剂B,催化剂物性见表1。
实施例3
制备含磷拟薄水铝石M,M中含有占其总重量2.01%的P。用氮气吸附法测定含磷拟薄水铝石M的比表面积和孔体积,M的比表面积为230m2/g,孔体积1.5mL/g,最可几孔径为19.5nm。
称取上述拟薄水铝石M100g(干基),加入田菁粉3g,将1.6g硼酸和0.8g聚氧乙烯醚溶解于110g去离子水中,加入前述物料中,混捏后在单螺杆挤条机上挤成直径3.0mm的四叶草形,110℃干燥4小时,再750℃焙烧4小时,得到氧化铝载体,配制含有(6.2gMoO3+2.6gNiO)/100mL的金属浸渍液,以饱和浸渍的方法对所得载体进行浸渍,在90℃下干燥6h,在500℃下焙烧5h,制得催化剂C,催化剂物性见表1。
实施例4
制备含磷拟薄水铝石M,M中含有占其总重量1.59%的P。用氮气吸附法测定含磷拟薄水铝石M的比表面积和孔体积,M的比表面积为240m2/g,孔体积1.5mL/g,最可几孔径为21.2nm。
称取上述拟薄水铝石M100g(干基),加入田菁粉3g,将1.8g氧化硼和1.2g聚氧乙烯醚溶解于110g去离子水中,加入前述物料中,混捏后在单螺杆挤条机上挤成直径2.0mm的圆柱形,60℃干燥10小时,再800℃焙烧4小时,得到氧化铝载体,配制含有(6.1gWO3+2.3gCo2O3)/100mL的金属浸渍液,以饱和浸渍的方法对所得载体进行浸渍,在60℃下干燥8h,在560℃下焙烧4h,制得催化剂D,催化剂物性见表1。
比较例1
称取商用的大孔拟薄铝石干胶粉(干基含量71.5wt%)100g,加入2.1g田菁粉和4.2g硼酸,混合均匀;将3.6g乙酸溶解于86g去离子水中,加入前述物料,混捏后在单螺杆挤条机上挤成直径2.5mm的圆柱形。在80℃干燥8小时,再于600℃焙烧4小时,得到氧化铝载体。配制含有(6.3gWO3+3.6gNiO+1.5P2O5)/100mL的金属浸渍液,以饱和浸渍的方法对所得载体进行浸渍,在85℃下干燥6h,在600℃下焙烧4h,制得催化剂B,催化剂物性见表1。
比较例2
将34.1g氢氧化铝干胶粉(含氧化铝75%的烷基铝水解产物)和硫酸铝法制得的氢氧化铝39.3g混合后加入聚氧乙烯醚3.5g和2.1g醋酸、66mL水混捏,在单螺杆挤条机上挤成直径3.0mm的三叶草形。在100℃干燥5小时,再于600℃焙烧4小时,得到氧化铝载体。配制含有(10.2gMoO3+1.6gNiO+0.8P2O5)/100mL的金属浸渍液,以饱和浸渍的方法对所得载体进行浸渍,在85℃下干燥5h,在600℃下焙烧4h,制得催化剂B,催化剂物性见表1。
采用BET和XRF等分析方法对煤焦油加氢预处理催化剂进行分析,结果见表1。
表1煤焦油加氢预处理催化剂物化性质
项目 | A | B | C | D | E | F |
比表面积,m<sup>2</sup>/g | 218 | 206 | 210 | 202 | 174 | 167 |
孔体积,mL/g | 0.98 | 1.01 | 1.02 | 1.12 | 0.66 | 0.62 |
最可几孔径,nm | 20.8 | 22.3 | 22.4 | 21.2 | 13.7 | 11.7 |
20~30nm孔分布,% | 48.9 | 51.8 | 55.3 | 62.9 | 7.9 | 4.1 |
MO<sub>3</sub>或WO<sub>3</sub>,% | 6.1 | 8.1 | 6.2 | 5.8 | 6.0 | 8.9 |
NiO或Co<sub>2</sub>O<sub>3</sub>,% | 4.6 | 3.5 | 2.4 | 2.1 | 2.8 | 1.5 |
强度,N/mm | 22.1 | 20.3 | 18.7 | 16.7 | 12.4 | 8.2 |
表1的结果表明,与比较例相比较,本发明方法制备的煤焦油加氢预处理催化剂孔容、孔径更大,最可几孔径为15~30nm,20~30nm以上大孔的孔体积占总孔容的45~70%;含硼化合物和聚氧乙烯醚的复合扩孔作用更好,孔径孔容更大;本发明方法制备的氧化铝载体,强度更高,满足工业应用要求。
在200ml小型评价装置上对上述实施例与对比例所得催化剂进行评价试验,对表1催化剂进行活性和稳定性评价,评价条件见表2,评价结果见表3。
表2催化剂评价条件
原料油性质 | 中低温煤焦油 |
密度(20℃),kg/m<sup>-3</sup> 1020 | 0.9923 |
金属,μg/g<sup>-1</sup> | 186 |
工艺条件 | |
反应温度,℃ | 300 |
氢分压,MPa | 10.0 |
体积空速h<sup>-1</sup> | 0.6 |
氢油比 | 800 |
表3催化剂金属脱除率
由表3评价结果可知,本发明催化剂具有更高的脱金属活性和更优的活性稳定性。
Claims (10)
1.一种煤焦油加氢预处理催化剂,其特征在于,所述催化剂以氧化铝为载体,孔容为0.9~1.5mL/g;比表面积为200~300m2/g;最可几孔径为15~30nm;20~30nm以上大孔的孔体积占总孔容的45~70%,其中,所述氧化铝载体采用的复合扩孔剂为含硼化合物和聚氧乙烯醚。
2.根据权利要求1所述的催化剂,其特征在于,以VIB和VIII金属元素为活性组分,加氢预处理催化剂中活性组分以金属计的重量含量为0.4%~10%,以磷元素为助剂,助剂磷以元素计的重量含量为0.1%~10%。
3.一种根据权利要求1-2任一项所述的煤焦油加氢预处理催化剂的制备方法,其特征在于,包括如下步骤:
(1)采用滴定法制备出铝水化合物,在搅拌条件下加入含磷化合物,然后静置、冷却、洗涤、干燥得到含磷拟薄水铝石M;
(2)将含磷拟薄水铝石M与复合扩孔剂和助挤剂混合并成型、干燥、焙烧制得氧化铝载体;
(3)配制含有钼和/或钨,和镍和/或钴的金属溶液,并对(2)中所得载体以饱和浸渍的方式负载金属;物料洗涤、在50~120℃下干燥2~4小时,然后在400~700℃下焙烧2~6小时,催化剂中含有占催化剂总重量0.4%~10%的活性金属,磷元素含量占催化剂总重量的0.1%~10%。
4.根据权利要求3所述的制备方法,其特征在于,所述的含磷拟薄水铝石M孔容为1.1~2.2mL/g,比表面积为130~500m2/g,最可几孔径为15~35nm。
5.根据权利要求3所述的制备方法,其特征在于,所述的复合扩孔剂为含硼化合物和聚氧乙烯醚。
6.根据权利要求3所述的制备方法,其特征在于,所述的聚氧乙烯醚为烷基酚聚氧乙烯醚、蓖麻油聚氧乙烯醚、脂肪胺聚氧乙烯醚、脂肪酸聚氧乙烯酯其中的一种或几种。
7.根据权利要求3所述的制备方法,其特征在于,所述的聚氧乙烯醚的加入量优选为拟薄水铝石干胶粉中对应的氧化铝重量的0.5~3%。
8.根据权利要求3所述的制备方法,其特征在于,所述的含硼化合物优选硼酸、氧化硼和硼酸盐中的一种或几种;以硼计,所述的含硼化合物的加入量优选为拟薄水铝石干胶粉中对应的氧化铝重量的0.5~5%。
9.根据权利要求3所述的制备方法,其特征在于,所述的助挤剂优选为田菁粉或淀粉,所述的助挤剂的加入量优选为拟薄水铝石干胶粉中对应的氧化铝重量的1~3%。
10.根据权利要求1-2任一项所述的催化剂用于重油加工用的加氢保护剂、脱金属催化剂和脱沥青质催化剂等加氢催化剂。
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