CN114405461B - 一种核壳式混晶煤基费托合成油烷烯分离吸附剂的制备方法 - Google Patents
一种核壳式混晶煤基费托合成油烷烯分离吸附剂的制备方法 Download PDFInfo
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
- C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
-
- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
- C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明公开了一种核壳式混晶煤基费托合成油烷烯分离吸附剂的制备方法。本发明制备方法包括以成型后的5A分子筛为吸附剂内核,通过添加硅源、铝源、无机碱在吸附剂内核表面水热晶化生成X分子筛壳层,制得核壳式混晶吸附剂前体后经碱金属盐溶液离子交换处理后即可制得可用于费托合成油模拟移动床烷烯分离工艺的核壳式混晶吸附剂。本发明吸附剂具有吸附容量高,α‑烯烃选择性高,吸脱附速率快,解吸剂用量少,分离能耗低等特点,采用本发明制备的吸附剂能显著降低α‑烯烃在吸附分离过程中的异构化率,实现α‑烯烃、异构烯烃以及烷烃的高效同步分离。
Description
技术领域
本发明涉及吸附分离技术领域,具体涉及一种核壳式混晶煤基费托合成油烷烯分离吸附剂的制备方法。
背景技术
费托(F-T)合成油是煤基清洁高效利用目前最有效的途径之一,F-T过程主要包括煤制合成气、合成气费托合成以及合成油品的精制加工三个主要的步骤。截止2017年,我国已经建成包括内蒙古伊泰、山西潞安、宁夏神华和上海兖矿等多套F-T合成油项目,产量将近10000KMTA,预计到2020年国内费托合成油项目的产能将达到20000KMTA。
工业上F-T合成油技术主要采用流化床高温合成与固定床低温合成两种工艺,两种工艺除了温度有所不同外,最主要的是产品分布不同。高温技术以生产汽油、轻烃为主,低温技术以生产柴油和蜡为主。低温F-T合成油的组分复杂,主要包括α-烯烃、正构烷烃以及醇、酮、醛和酯等含氧化合物,对于低温合成费托油中,通常α-烯烃质量分数为40~60%,氧化物的质量分数为3~10%。α烯烃是双键在分子链端部的单烯烃,是石油化学工业重要的基础原料之一,通过石化和煤化工路线生产,在制备线性低密度聚乙烯、线性高密度聚乙烯、工业用合成润滑油剂、异壬醇、异癸醇、洗涤剂等方面具有重要的用途。F-T粗油品主要用于初级化工原料或者燃料油使用,在油价长期处于较低价位时经济效益不高,市场竞争力不强。如果将F-T合成油中的长链α-烯烃进行分离,不仅可以获得具有高附加值的长链烯烃,还可以生产清洁优质的航空煤油、润滑油基础油或特种溶剂油等具有较高附加值的产品,从而提高煤基F-T合成油现有技术的经济性和抵御市场风险的能力。
目前通过煤基费托油生产α烯烃一般通过萃取精馏工艺以及吸附分离工艺两种方式,其中萃取精馏工艺对精馏塔板层数要求高,设备投资大,萃取精馏过程分离能耗大,吸附分离工艺一般采用X分子筛或A型分子筛作为吸附剂,其中X分子筛硅铝比一般在2.5~3.0,硅铝比低于2.5的X分子筛合成过程中结晶度较低,吸附容量较低,吸附原料处理量偏低,硅铝比2.0的X分子筛经Li+交换后可用于空气中的N2、O2分离,A型分子筛则根据不同种类的阳离子交换改变孔径尺寸,一般用于C2~C6正异构烃类的吸附分离。
USP2866835应用5A分子筛在80~230℃的温度下分离催化汽油中C6~C7馏分段的烯烃组分,可将原料中约4%左右的烯烃富集至55%的浓度。该工艺采用固定床吸附分离,丁烯做解吸剂,需间歇操作,另外该方法富集的烯烃浓度较低,且为混合烯烃,利用价值较低。
USP3510423以C10~C15烷烃和烯烃的混合物为原料,通过8个床层的模拟移动床吸附分离工艺分离出烯烃,吸附剂采用Ag交换的X或Y型分子筛,烯烃产品的纯度可以达到98%。该方法提供的吸附剂具有较好的烯烃分离度,但解吸剂用量较大,分离能耗较大。
CN101652339B公开了一种分离C4烯烃的工艺,进料包括正丁烯、异丁烯、正丁烷和异丁烷等组分,采用间歇吸附分离工艺得到较高纯度的正构C4烯烃。该方法仅能分离特定馏分段中烯烃组分,工业应用前景欠佳。
CN101462919B公开了一种生产清洁剂用烯烃的分离方法,吸附分离的原料为C9~C20的烷烃和烯烃的混合物,解吸剂采用C6~C8的环烷烃。吸附分离工艺采用模拟移动床吸附分离方法。
CN109627137B采用萃取精馏的方式从煤基费托合成轻质馏分油中分离烯烃,烯烃纯度可达99.7%,但该法工艺流程复杂,萃取剂用量大,工艺能耗极高,且仅可分离单一组分的烯烃。
现有烷烯分离吸附剂普遍存在吸附选择性低的问题,无法满足生产高纯度α-烯烃的要求。为解决现有技术中存在的问题,需要提出一种生产工艺简便、生产成本低、α-烯烃产品纯度高、原料适用范围广的高纯α-烯烃分离的吸附剂的制备方法。
发明内容
本发明涉及一种核壳式混晶煤基费托合成油烷烯分离吸附剂的制备方法,目的在于克服现有技术不足,提供一种用于煤基费托合成油烷烯分离制备高纯α-烯烃的吸附剂的制备方法,该吸附剂具有吸附容量高,α-烯烃选择性高,吸脱附速率快,解吸剂用量少,分离能耗低等特点。
本发明一种用于煤基费托合成油烷烯分离制备高纯α-烯烃的吸附剂的制备方法包括如下步骤:
(1)将5A沸石分子筛、粘结剂及助剂混合后聚结成颗粒物,干燥、焙烧,作为吸附剂内核;
(2)将步骤(1)所得的吸附剂内核,加入硅源、铝源、无机碱、去离子水进行X分子筛壳层水热晶化,得到核壳式混晶吸附剂前体;
(3)将步骤(2)所得混晶吸附剂用碱金属或碱土金属的盐溶液在80~95℃处理,进行阳离子交换,进一步降低沸石分子筛的酸性,降低其对α-烯烃的异构化率。
本发明提供的方法,步骤(1)中聚结方法为挤条成型或滚球成型。
本发明提供的方法,步骤(1)中所述的粘结剂为高岭土、凹凸棒土、硅溶胶中的一种或几种。
本发明提供的方法,步骤(1)中所述的助剂为田菁粉、可溶性淀粉和羧甲基纤维素中的一种或几种。
本发明提供的方法,步骤(2)中所述的硅源为水玻璃、硅溶胶、白炭黑中的一种或者其任意比例的组合,所述的铝源为偏铝酸钠及可溶性铝盐中任一种或者其任意比例的组合,所述的无机碱为氢氧化钠或氢氧化钾中的一种。
本发明提供的方法,步骤(2)中所述的水热晶化物料计算包含粘结剂及添加的硅源、铝源、无机碱,去离子水,物料比例为SiO2/Al2O3=2.1~3.3,Na2O/SiO2=1.1~2.1,H2O/SiO2=30~80。
本发明提供的方法,步骤(2)中所述的X分子筛壳层水热晶化温度为80~100℃,晶化时间为4~24h;
本发明提供的方法,步骤(2)中所述的X分子筛壳层占混晶吸附剂质量分数为20%~70%。
本发明提供的方法,步骤(2)中所述的X分子筛壳层硅铝比为2.0~3.0,晶粒粒径为0.1~5.0μm,更优选的硅铝比为2.2~2.5,晶粒粒径为0.8~2.5μm。
本发明提供的方法,步骤(3)中所述的无机碱溶液选自氢氧化钠、氢氧化钾中的一种或者其任意比例的混合,所述的无机碱溶液浓度为0.05~2.0mol/L,所述的碱金属或碱土金属的盐溶液选自氯化锂、硝酸铯、氯化锶、硫酸钡中的至少一种,经阳离子交换后其对应的氧化物含量占混晶吸附剂的0.01~5%。
本发明具有以下创新点和优势:
1、本发明针对煤基费托合成油中α-烯烃含量高、存在少量异构烯烃的特点,提供一种A型分子筛和X分子筛复合的核壳式混晶改性吸附剂,可用于费托合成油烷烯分离模拟移动床工艺,显著提高α-烯烃产品的纯度,降低α-烯烃在吸附分离过程中的异构化率,实现α-烯烃、异构烯烃以及烷烃的高效同步分离;
2、该吸附剂具有吸附容量高,α-烯烃选择性高,吸脱附速率快,解吸剂用量少,分离能耗低等特点。
具体实施方式
为了使本发明实现的技术手段、创新特征、达成目的与功效易于明白了解,下面结合具体实施例,进一步阐述本发明,但本发明并不仅限于此。
实施例中吸附剂的评价性能数据的测定方法为:
吸附剂的分离性能通过动态脉冲试验来计算。单柱动态脉冲试验可用于测定吸附剂的分离系数和表征吸脱附速率,是评价吸附剂性能的主要方法之一。实验室采用一根规格为Φ10×1mm、长1200mm的不锈钢直管为吸附柱,吸附剂装填量为60ml,采用油浴加热和保温,吸附柱上端入口与进料相连,下端出口接背压阀与流出物收集器连接。原料和解吸剂经微量柱塞泵送入吸附柱,背压阀控制系统压力,流出物经空冷后收集。吸附剂试验所用脉冲液原料为质量分数30%己烯-1+30%辛烯-1+20%正己烷+20%正辛烷,以及30%十二烯-1+30%十四烯-1+20%十二烷+20%十四烷,对应上述两种脉冲液,解吸剂分别为正癸烷或正辛烷,目的为与脉冲液存在沸点差,方便解吸剂的分离和回用。
动态脉冲试验方法为,将活化后的吸附剂装入吸附柱震荡填实,然后通入解吸剂排除系统中的气体,将压力升至1.0MPa,再逐渐升温至指定温度。然后快速通入6ml的脉冲液进料,继续通入解吸剂并以同样的空速进行脱附,解吸液每进料5min取一份脱附液样品,用气相色谱分析组成。以脱附用解吸剂进料体积为横坐标,脉冲液各组分浓度为纵坐标,可以绘制出上述各组分含量随解吸剂用量而变化的峰形曲线。该曲线给出了各组分半峰宽中点到零点的解吸液进料体积,即保留体积VR,任意组分的保留体积与吸附平衡时的分配系数成正比,它反映了各组分吸附平衡情况,两组分净保留体积之比即吸附选择性β值,也称为分离系数。β值越大,说明两组分分离的越好。各组分包络线的半峰宽W1/2则提供了传质速率的信息,半峰宽越窄,说明吸附剂对该组分的吸脱附速率越快。
实施例1
制备本发明核壳式混晶吸附剂并进行性能测试。
(1)挤条成型:将100克纯5A分子筛(骨架中SO2/Al2O3氧化铝摩尔比为2.60、平均晶粒粒径1.2μm、相对结晶度91%的5A分子筛,含水率24%)与17克高岭土(含水率15%)和1g羧甲基纤维素混合均匀,然后加入适量的去离子水混合均匀,挤条成型(直径Φ2)。破碎后取直径为20~50目标准筛的颗粒,120℃空气下烘干12h,550℃焙烧4h制得吸附剂内核55.8g。
(2)水热晶化:将步骤(1)中制得的吸附剂内核加入水热合成体系中进行水热晶化合成X分子筛壳层,其中水热合成体系投料为水玻璃39.4g(SiO2质量分数为22.63%,Na2O质量分数为6.97%),偏铝酸钠9.36g,氢氧化钠5.19g,去离子水120.53g,100℃水热晶化6h后以去离子水洗涤至流出液pH值<10,120℃空气下烘干12h,550℃焙烧4h制得核壳式混晶吸附剂前体67.13g,其中X分子筛壳层占吸附剂前体质量分数为20.3%。
(3)碱处理:将步骤(2)中制得的核壳式混晶吸附剂,以液固比5:1的比例置于0.05mol/L氯化锂溶液中,80℃静置浸泡12h,洗涤、干燥焙烧后制得核壳式混晶吸附剂A-1单柱脉冲试验采用30%己烯-1+30%辛烯-1+20%正己烷+20%正辛烷为脉冲液,正癸烷为解吸剂,测得的吸附剂吸附性能见表1所示。
实施例2
按实施例1的方法制备吸附剂,不同的是(1)步所用粘结剂为凹凸棒土(含水率15%),制得吸附剂内核60.3g,(2)步水热合成体系投料为硅溶胶48.9g(SiO2质量分数为28.6%),偏铝酸钠12.48g,氢氧化钾6.92g,去离子水160.71g,90℃水热晶化12h,制得核壳式混晶吸附剂前体83.33g,其中X分子筛壳层占吸附剂前体质量分数为38.2%,(3)步所用的硝酸铯溶液浓度为0.5mol/L,85℃静置浸泡9h,制得吸附剂A-2,单柱脉冲试验采用30%己烯-1+30%辛烯-1+20%正己烷+20%正辛烷为脉冲液,正癸烷为解吸剂,测得的吸附剂吸附性能见表1所示。
实施例3
按实施例1的方法制备吸附剂,不同的是(1)步所用粘结剂为硅溶胶(固含量25%),制得吸附剂内核57.4g,(2)步水热合成体系投料为白炭黑10.53g,氢氧化铝21.77g,氢氧化钠9.54g,去离子水160.71g,80℃水热晶化24h,制得核壳式混晶吸附剂前体88.22g,其中X分子筛壳层占吸附剂前体质量分数为53.7%,(3)步所用的氯化锶溶液浓度为1mol/L,90℃静置浸泡6h,制得吸附剂A-3,单柱脉冲试验采用30%己烯-1+30%辛烯-1+20%正己烷+20%正辛烷为脉冲液,正癸烷为解吸剂,测得的吸附剂吸附性能见表1所示。
实施例4
按照实施例1的方法制备吸附剂,不同的是吸附剂内核采用滚动成型的方式制备20~40目的球形颗粒48.5g,(2)步水热合成体系投料为水玻璃78.78g(SiO2质量分数为22.63%,Na2O质量分数为6.97%),偏铝酸钠18.72g,氢氧化钠10.38g,去离子水241.08g,80℃水热晶化24h,制得核壳式混晶吸附剂前体82.35g,其中X分子筛壳层占吸附剂前体质量分数为69.8%,(3)步所用的硫酸钡溶液浓度为2.0mol/L,95℃静置浸泡2h,制得吸附剂A-4,单柱脉冲试验采用30%十二烯-1+30%十四烯-1+20%十二烷+20%十四烷为脉冲液,正辛烷为解吸剂,测得的吸附剂吸附性能见表1所示。
实施例5
按实施例4的方法制备吸附剂,不同的是(1)步所用粘结剂为凹凸棒土(含水率15%),制得吸附剂内核65.4g,(2)步水热合成体系投料为硅溶胶75.62g(SiO2质量分数为28.6%),偏铝酸钠12.46g,氢氧化钠15.48g,去离子水238.34g,90℃水热晶化12h,制得核壳式混晶吸附剂前体103.9g,其中X分子筛壳层占吸附剂前体质量分数为58.9%,(3)步所用的硝酸铯溶液浓度为0.5mol/L,85℃静置浸泡9h,制得吸附剂A-5,单柱脉冲试验采用30%十二烯-1+30%十四烯-1+20%十二烷+20%十四烷为脉冲液,正辛烷为解吸剂,测得的吸附剂吸附性能见表1所示。
表1
实施例号 | 1 | 2 | 3 | 4 | 5 |
吸附剂编号 | A-1 | A-2 | A-3 | A-4 | A-5 |
β己烯-1/正己烷 | 1.58 | 1.67 | 1.74 | - | - |
β辛烯-1/正辛烷 | 1.46 | 1.52 | 1.53 | - | - |
己烯-1半峰宽,mL | 32.97 | 31.68 | 33.88 | - | - |
辛烯-1半峰宽,mL | 20.51 | 20.32 | 22.14 | - | - |
β十二烯/十二烷 | - | - | - | 1.85 | 1.88 |
β十四烯/十四烷 | - | - | - | 1.58 | 1.61 |
十二烯半峰宽,mL | - | - | - | 33.87 | 32.54 |
十四烯半峰宽,mL | - | - | - | 21.69 | 21.30 |
解吸剂种类 | 正癸烷 | 正癸烷 | 正癸烷 | 正辛烷 | 正辛烷 |
Claims (6)
1.一种核壳式混晶煤基费托合成油烷烯分离吸附剂的制备方法,其特征在于,包括如下步骤:
1)将5A沸石分子筛、粘结剂及助剂混合后聚结成颗粒物,干燥、焙烧,作为吸附剂内核;
2)将步骤1)所得的吸附剂内核,加入硅源、铝源、无机碱、去离子水进行X分子筛壳层水热晶化,得到核壳式混晶吸附剂前体;所述的X分子筛壳层占混晶吸附剂质量分数为20%~70%;
3)将步骤2)所得混晶吸附剂前体用碱金属或碱土金属的盐溶液在80~95℃处理,进行阳离子交换,经洗涤、干燥焙烧后制得;其中碱金属或碱土金属氧化物含量占混晶吸附剂的0.01~5%;
其中,步骤2)中所述的硅源为水玻璃、硅溶胶、白炭黑中的一种或者其任意比例的组合,所述的铝源为偏铝酸钠及可溶性铝盐中任一种或者其任意比例的组合,所述的无机碱为氢氧化钠或氢氧化钾中的一种或者其任意比例的组合,所述的无机碱溶液浓度为0.05~2.0mol/L;
所述步骤2)中所述的水热晶化物料计算包含粘结剂及添加的硅源、铝源、无机碱,去离子水,物料比例为SiO2/Al2O3=2.1~3.3,Na2O/SiO2=1.1~2.1,H2O/SiO2=30~80;
步骤2)中所述的X分子筛壳层水热晶化温度为80~100℃,晶化时间为4~24h;
步骤3)中所述的碱金属或碱土金属的盐溶液选自氯化锂、硝酸铯、氯化锶、硫酸钡中的至少一种。
2.根据权利要求1所述的制备方法,其特征在于,步骤1)中聚结方法为挤条成型或滚球成型。
3.根据权利要求1所述的制备方法,其特征在于,步骤1)中所述的粘结剂为高岭土、凹凸棒土、硅溶胶中的一种或几种。
4.根据权利要求1所述的制备方法,其特征在于,步骤1)中所述的助剂为田菁粉、可溶性淀粉和羧甲基纤维素中的一种或几种。
5.根据权利要求1所述的制备方法,其特征在于,步骤2)中所述的X分子筛壳层硅铝比为2.0~3.0,晶粒粒径为0.1~5.0μm。
6.根据权利要求1所述的制备方法,其特征在于,所述的X分子筛壳层的硅铝比为2.2~2.5,晶粒粒径为0.8~2.5μm。
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