CN1034223C - 制取低碳烯烃的裂解催化剂 - Google Patents

制取低碳烯烃的裂解催化剂 Download PDF

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CN1034223C
CN1034223C CN93102783A CN93102783A CN1034223C CN 1034223 C CN1034223 C CN 1034223C CN 93102783 A CN93102783 A CN 93102783A CN 93102783 A CN93102783 A CN 93102783A CN 1034223 C CN1034223 C CN 1034223C
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zeolite
heavy
described catalyzer
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rare earth
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CN1093101A (zh
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施至诚
施文元
叶忆芳
葛星品
曹平
刘舜华
谢朝纲
李再婷
舒兴田
杨小明
付维
周蒙
何鸣元
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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China Petrochemical Corp
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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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/26—After treatment, characterised by the effect to be obtained to stabilize the total catalyst structure
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite

Abstract

一种用于生产低碳烯烃的裂解催化剂，是由0～70%(以催化剂重量为基准计)的粘土、5～99%的无机氧化物和1～50%的沸石组成，其中的沸石为0～25重%的REY或高硅Y型沸石和75～100重%的含磷和稀土的五元环高硅沸石的混合物。该催化剂具有较以HZSM-5沸石为活性组分的催化剂更高的水热活性稳定性、转化率和C2 ＝～C4 ＝产率。

Description

制取低碳烯烃的裂解催化剂
本发明涉及用于石油烃裂解制取低碳烯烃的催化剂。具体地说，本发明涉及用于石油烃裂解制取乙烯、丙烯和丁烯，主要是丙烯和丁烯的含结晶硅铝酸盐沸石的催化剂。
低碳烯烃是重要的石油化工原料，普遍采用的制取方法是以天然气为原料的蒸汽裂解；以石脑油或轻柴油为原料的管式炉热裂解；重质烃的热载体裂解以及用低碳醇催化转化的方法。常规的催化裂化装置在生产汽油及轻柴油的同时也付产烯烃，其产量占原料油的15重％以下。
从文献看，以石油烃为原料采用裂化或裂解方法制取低碳烯烃时所使用的催化剂大致有三类：一类是以氧化物为载体的金属负载型催化剂，它们的载体可以是SiO2、Al2O3或其它氧化物，所负载的金属元素多属IIB、VB、VIIB和VII族元素(USP3,541,179；USP3,647,682；DD225,135；SU1,214,726)。使用这类催化剂时由于所负载金属的脱氢性能，在进行裂化反应的同时聚合结焦反应也相应加快，因此采用此类催化剂时只能使用轻质原料(＜220℃)。
所使用的第二类催化剂是复合氧化物。如以ZrO2和/或HfO2为主要成分，辅以Al2O3、Cr2O3、MnO和/或Fe2O3以及碱金属或碱土金属氧化物(USP3,725,495；USP3,839,485)。又如以钒酸钾、锡酸钾或铌酸钾为催化剂，汽油裂解后可得约56重％的低碳烯烃，乙烯产率可达36.5重％，丙烯产率为12.5重％(SU523，133；SU487，927；SU410，073)。再如含少量Fe2O3、TiO2、CaO、MgO、Na2OK2O的SiO2·Al2O3催化剂用于各种烃馏分的裂解(SU550，173；SU559，946)。较常用的复合氧化物是无定形SiO2·Al2O3，DD152，356中披露了以无定形SiO2·Al2O3为催化剂，以液态烃或各种烃馏份(包括汽油、煤油、瓦斯油或减压馏份油)为原料，在600～800℃的反应温度下制取低碳烯烃，C2 ＝～C4 ＝的产率可达40～55重％。
随着沸石在石油化工和石油加工领域中日益广泛的应用，大量的文献报导了第三类催化剂，即含沸石的催化剂，特别是含ZSM-5择形沸石的催化剂。这类催化剂既可单独使用也可做为添加剂引入催化裂化装置或裂化催化剂中。如JP60-224，428中披露了用ZSM-5沸石为活性组分、Al2O3为载体的催化剂，在600～750℃下对C5～C25的石蜡烃原料进行催化裂化，C2 ＝～C4 ＝的产率为30％左右。USP4,309,280中披露了将占催化剂重0.01～1％的HZSM-5沸石直接加入催化裂化反应装置中。USP3,758,403中披露了以ZSM-5沸石和大孔沸石(如X型、Y型)为活性组分(二者的比例为1∶10～3∶1)的催化剂可在提高产物汽油辛烷值的同时使C3 ＝＋C4 ＝的产率增加至10重％左右。本申请人也曾在CN1004878B、USP4,980,053和CN1043520A中披露了以ZSM-5沸石和Y型沸石的混合物为活性组分的催化剂，在500～650℃的反应温度下，可在提高产物汽油辛烷值的同时提高C2 ＝～C4 ＝的产率，且其中以C3 ＝和C4 ＝为主要产物。
本发明旨在提供一种新型沸石催化剂，它具有较以HZSM-5沸石为活性组分的催化剂更高的水热活性稳定性、转化率和C2 ＝～C4 ＝产率。
本发明提供的催化剂具有下列组成：0～70％(以催化剂重量为基准计)的粘土、5～99％的无机氧化物和1～50％的沸石，所说沸石为0～25重％的Y型沸石和75～100重％的含磷和稀土的五元环高硅沸石的混合物。
本催化剂中的粘土可以是天然的或人工合成的、经或不经各种化学和/或物理处理的、通常用作裂化催化剂载体的各种粘土，如高岭土、多水高岭土等。
本催化剂中的无机氧化物选自无定形SiO2·Al2O3、Al2O3和/或SiO2。
本催化剂中的Y型沸石可以是经稀土金属离子交换后得到的稀土含量(以RE2O3计)不低于14重％的REY沸石，也可以是经各种化学和/或物理方法，如水热法、酸处理法、抽铝补硅法、SiCl4法等处理后得到的硅铝比较高、稳定化了的高硅Y型沸石。
本催化剂中的含磷和稀土的五元环高硅沸石是用磷酸铝处理得的含稀土的五元环高硅沸石，该沸石中含磷(以P2O5计)2～20重％，最好2～10重％，含稀土(以RE2O3计)2～10重％。
含稀土的五元环高硅沸石(商品牌号ZRP)具有ZSN-5沸石族的X光衍射谱图，其无水化学组成表达式为：0.01～0.30RE2O3·0.4～1.0Na2O·Al2O3·20～60SiO2，该组成中的稀土来自合成时所用的含稀土的八面沸石晶种，该沸石的孔道较ZSM-5沸石为窄，它对正己烷与环己烷的吸附量的比值是ZSM-5沸石的2～4倍。该沸石是用CN1058382A或美国专利申请号07/820,385或欧洲专利申请号92200061.7中所披露的方法制备得的，即以水玻璃、磷酸铝、无机酸为原料，以REY或REHY沸石为晶种，在130～200℃下晶化反应12～60小时制成的。
用磷酸铝处理ZRP沸石的方法如下：将沸石用铵离子进行预交换处理使其钠含量(以Na2O计)降至不大于0.1重％，将组成为Al2O3∶P2O5＝1∶1～3的磷酸铝胶体按照P2O5∶沸石(干基)＝1∶5～99的重量比与该沸石混合均匀，于300～600℃、10～100％水蒸汽存在下焙烧0.5～6小时。
本发明提供的催化剂制法如下：将无机氧化物的前身物，如铝溶胶、拟薄水铝石、硅溶胶或其混合物以及硅铝溶胶或凝胶，与粘土按预定配比混合，并用脱阳离子水将其配制成固含量为10～50重％的浆液，搅拌均匀，用无机酸，如盐酸、硝酸、磷酸、硫酸将浆液PH调至2～4，保持该PH值，于20～80℃下静置老化0～2小时后加入预定量的沸石，均质，喷雾干燥，洗去游离钠离子，干燥。
本发明提供的催化剂用于催化裂解时较用HZSM-5沸石为活性组分的催化剂具有水热活性稳定性高、转化率高、重油转化率高和C2 ＝～C4 ＝产率高的特点。例如在微反装置上用直馏柴油为原料，在520℃、剂油比3.2、重量空速16时-1的条件下进行裂解性能评定时，样品经800℃、100％水蒸汽处理4小时后，本发明提供的催化剂较用HZSM-5沸石为活性组分的催化剂的活性保留度高7～25个单位；即使样品经800℃、100％水蒸汽处理17小时后，前者仍比后者高8～14个单位。又如在小型固定流化床装置上用中间基蜡油为原料，在580℃、剂油比5、重量空速1时-1的条件下进行裂解性能评定时，本发明提供的催化剂较用HZSM-5沸石为活性组分的催化剂转化率高4～7个单位、重油转化率高3.5～8个单位、C2 ＝～C4 ＝产率高4～5个单位。
下面的实例将对本发明予以进一步的说明。
实例中所用含磷和稀土的五元环高硅沸石(以下简记为P-ZRP)的制备如下：取100克(干基)ZRP沸石(山东周村催化剂厂产品，SiO2/Al2O3 30，RE2O3 2.0％)，按照沸石(干基)∶硫酸铵∶脱阳离子水＝100∶25∶2000的重量比在90℃下离子交换1小时，过滤后再交换1次。原子吸收光谱测得该沸石中钠含量(以Na2O计)为0.04％。将13.8克拟薄水铝石(山东铝厂产品，Al2O3 95％，固含量30％)、9.0克工业磷酸(含量85％)与200克脱阳离子水混和均匀后加入上述铵交换得的沸石中，搅拌均匀，110℃干燥后在800℃、100％水蒸汽气氛中老化4小时即得磷含量(以P2O5计)为5％的含磷和稀土的五元环高硅沸石P-ZRP。
实例中采用小型固定流化床装置评价催化剂时的条件为：反应温度580℃，剂油比5，重量空速1时-1，注水量20％。催化剂样品预先经760℃、100％水蒸汽处理6小时，其装量为180克。反应所用原料中间基蜡油的性能如下：
密度(20℃)，克/厘米3   0.8808
康氏残炭，重％          0.26
H/C(原子比)             1.79
S                       0.33
N                       0.14
碱氮，ppm               537
馏程，℃                256～545
K                       12.0
实例中采用微反装置评价催化剂时的条件为：反应温度520℃，剂油比3.2，重量空速16时-1，进料时间70秒。催化剂样品预先经800℃、100％水蒸汽处理4小时，其装量为5.0克。反应所用原料直馏柴油的性能如下：
馏程，℃        229～340
石蜡烃，重％    45.5
环烷烃，重％    35.7
芳烃，重％      18.2
胶质，重％      0.6
实例1～2
本发明提供的以P-ZRP沸石为活性组分，以粘土为基质、铝溶胶为粘结剂的催化剂的制备及其裂解性能。
在218公斤的铝溶胶(山东周村催化剂厂产品，Al2O3 11.4％，PH2～3)中加入147公斤多水高岭土(苏州瓷土公司工业产品，固含量80％)，搅拌90分钟，再加A36公斤(干基)P-ZRP沸石和54公斤脱阳离子水，均质，喷雾干燥成型即得催化剂样品A。
按同样的制备方法，将P-ZRP沸石用量减至20公斤制得催化剂样品B。
[对比例1]用HZSM-5沸石(山东周村催化剂厂产品，SiO2/Al2O3≮55，结晶度＞85％，Na2O＜0.05重％)代替P-ZRP沸石，按照样品A的原料用量和制备方法制得对比样品1。
上述三样品的组成及物化性能列于表1。在小型固定流化床装置和微反装置上对上述样品的评价结果分别列于表2和表3。
由表2可知：当催化剂中P-ZRP与HZSM-5含量相同时，本发明提供的催化剂较用HZSM-5为活性组分的催化剂转化率高约7个单位，重油转化率高约8个单位，C2 ＝～C4 ＝的产率高4.5个单位。当催化剂中P-ZRP的含量仅为HZSM-5含量的55％时，二者具有相近的重油转化活性和C2 ＝～C4 ＝收率。
由表3同样也可看出类似的结果。
表1
Figure C9310278300101
表2
表3
Figure C9310278300121
实例3～4
本发明提供的以P-ZRP沸石为活性组分，以粘土为基质、拟薄水铝石为粘结剂的催化剂的制备及其裂解性能。
用380公斤脱阳离子水将168公斤多水高岭土打浆，再加入174公斤拟薄水铝石和17公斤盐酸，搅拌均匀，在75℃下静置老化1小时，保持PH2～4，将温度降至60℃以下，加入30公斤(干基)P-ZRP沸石和50公斤脱阳离子水，均质，喷雾干燥成型，洗去游离Na+，干燥即得催化剂样品C。
按同样的制备方法，采用磷含量为3％的P-ZRP沸石制得催化剂样品D。
[对比例2]用HZSM-5沸石代替P-ZRP沸石，按照催化剂样品C的制备方法制得对比样品2。
上述三样品的组成及物化性能列于表4。在小型固定流化床装置上对上述样品的评价结果列于表5。
由表5可知：本发明提供的催化剂较用HZSM-5为活性组分的催化剂转化率高4～5.5个单位，重油转化率高3.5～5个单位，C2 ＝～C4 ＝的产率高约4个单位。
表4
Figure C9310278300131
表5
Figure C9310278300141
实例5
本发明提供的以P-ZRP沸石为活性组分，以无定形硅铝为基质的催化剂的制备及其裂解性能。
将373升水玻璃(山东周村催化剂厂产品，模数3.2±0.1，SiO2 124±2.0克/升)用398公斤的脱阳离子水稀释，加入97升Al2O3含量为50克/升的硫酸铝溶液(山东周村催化剂厂产品)，搅拌均匀，将其温度控制在15～25℃，再依次加人136升Al2O3含量为90克/升的硫酸铝溶液和95升氨水，搅拌均匀后将36公斤(干基)P-ZRP沸石和54公斤脱阳离子水加入上述基质胶体内均质，喷雾干燥成型，洗涤，干燥即得催化剂样品E。
[对比例3]用HZSM-5沸石代替P-ZRP沸石，按照上述样品的原料用量和制备方法制得对比样品3。
上述二样品的组成及物化性能列于表6。在小型固定流化床装置上对上述样品的评价结果列于表7。
由表7可知：本发明提供的催化剂较用HZSM-5为活性组分的催化剂C2 ＝～C4 ＝的产率高5个单位。
表6
表7
实例6～9
本发明提供的以P-ZRP和REY混合沸石为活性组分，以粘土为基质、拟薄水铝石为粘结剂的催化剂的制备及其裂解性能。
按照实例3～4中催化剂样品C的制备方法，以不同比例的P-ZRP和REY(山东周村催化剂厂产品，SiO2/Al2O3≮4.7，RE2O3≮17％)混合沸石为活性组分制备出催化剂样品F、G、H、I。
[对比例4]用HZSM-5沸石代替P-ZRP沸石制成以HZSM-5和REY混合沸石为活性组分的对比样品4。
上述5个样品的组成列于表8。在微反装置上对上述样品评价的结果列于表9。
由表9中沸石含量相同的样品G和对比样品4的数据可知：本发明提供的催化剂具有转化率高、C2 ＝～C4 ＝产率高的特点。
表8
    催化剂     F     G     H     I     对比4
组成，重％高岭土Al2O3P-ZRPREYHZSM-5 57.424.617.10.90 57.424.616.21.80 57.424.614.43.60 57.424.612.65.40 57.424.602.016.0
表9
Figure C9310278300181
实例10～13
本发明提供的以P-ZRP和高硅Y混合沸石为活性组分，以粘土为基质、拟薄水铝石为粘结剂的催化剂的制备及其裂解性能。
按照实例3～4中催化剂样品C的制备方法，以不同比例的P-ZRP和RSY(商品名，山东周村催化剂厂产品，系用脱铝补硅法制得的SiO2/Al2O3≮11的高硅Y)混合沸石为活性组分制备出催化剂样品J、K、L、M。
[对比例5]用HZSM-5沸石代替P-ZRP沸石制成以HZSM-5和RSY混合沸石为活性组分的对比样品5。
上述5个样品的组成列于表10。在微反装置上对上述样品评价的结果列于表11。
由表11中沸石含量相同的样品J和对比样5的数据可知：本发明提供的催化剂具有转化率高、C2 ＝～C4 ＝产率高的特点。
表10
    催化剂     J     K     L     M    对比5
组成，重％高岭土Al2O3P-ZRPRSYHZSM-5 57.424.617.10.90 57.424.616.21.80 57.424.614.43.60 57.424.612.65.40 57.424.600.917.1
表11
实例14
本发明提供的以P-ZRP沸石为活性组分，以粘土为基质、拟薄水铝石与硅溶胶为粘结剂的催化剂的制备及其裂解性能。
将82公斤硅溶胶(温州催化剂厂产品，SiO2 24.49重％，Na2O0.16重％)用184公斤脱阳离子水稀释，再加入114公斤多水高岭土、185公斤拟薄水铝石和12.5公斤盐酸，搅拌均匀，室温下静置老化30分钟，保持PH2～4，加入36公斤(干基)P-ZRP沸石和54公斤脱阳离子水均质，喷雾干燥成型，洗涤，干燥即得催化剂样品N。
[对比例6]用HZSM-5沸石代替P-ZRP沸石制成以HZSM-5沸石为活性组分的对比样品6。
二样品的组成及物化性能列于表12。在微反装置上对上述二样品评价的结果列于表13。
由表13可知：本发明提供的催化剂具有转化率高、C2 ＝～C4 ＝产率高的特点。
表12
Figure C9310278300201
表13
Figure C9310278300211
实例15
本发明提供的催化剂具有水热活性稳定性高的特点。
将催化剂样品C、D和对比样品2的新鲜样品，经800℃、100％水蒸汽老化处理4小时后的样品，经800℃、100％水蒸汽老化处理17小时后的样品分别在微反装置上评价其催化活性，结果分别列于表14、15和16。
表中的活性保留度％＝水热老化后活性/新鲜剂活性×100％
由表15可知：经800℃、100％水蒸汽老化处理4小时后，本发明提供的催化剂较用HZSM-5沸石为活性组分的催化剂的活性保留度高7～25个单位。由表16则可知：经800℃、100％水蒸汽老化处理17小时后，本发明提供的催化剂较用HZSM-5沸石为活性组分的催化剂的活性保留度仍然高8～14个单位。
表14
Figure C9310278300221
表15
表16

Claims (9)

1、一种用于生产低碳烯烃的裂解催化剂，是由0～70％(以催化剂重量为基准计)的粘土，5～99％的无机氧化物和1～50％的沸石组成，其特征在于所说沸石中含0～25重％的Y型沸石和75～100重％的含磷(以P2O5计)2～20重％、含稀土(以RE2O3计)2～10重％的五元环高硅沸石。
2、按照权利要求1所述的催化剂，其特征在于所说的无机氧化物选自SiO2·Al2O3、Al2O3和/或SiO2。
3、按照权利要求1所述的催化剂，其特征在于所说的Y型沸石是经稀土金属离子交换得的稀土含量(以RE2O3计)不低于14重％的REY沸石。
4、按照权利要求1所述的催化剂，其特征在于所说的Y型沸石是经化学和/或物理方法处理得的稳定化的高硅Y型沸石。
5、按照权利要求1所述的催化剂，其特征在于所说的含磷和稀土的五元环高硅沸石是用磷酸铝处理的含稀土五元环高硅沸石。
6、按照权利要求5所述的催化剂，其特征在于所说的含磷和稀土的五元环高硅沸石是用磷酸铝处理得的含磷(以P2O5计)2～10重％的含稀土五元环高硅沸石。
7、按照权利要求5或6所述的催化剂，其特征在于所说的含稀土五元环高硅沸石具有ZSM-5沸石族的X光衍射谱图，其无水化学表达式为0.01～0.30 RE2O3·0.4～1.0 Na2O·Al2O3·20～60SiO2，它对正己烷与环己烷吸附量的比值是ZSM-5沸石的2～4倍。
8、按照权利要求5或6所述的催化剂，其特征在于所说的含稀土五元环高硅沸石是以水玻璃、磷酸铝、无机酸为原料，以REY或REHY沸石为晶种，在130～200℃下晶化反应12～60小时制成的。
9、按照权利要求5或6所述的催化剂，其特征在于所说的用磷酸铝处理含稀土的五元环高硅沸石的方法如下：将沸石用铵离子进行预交换处理使其钠含量(以Na2O计)降至不大于0.1重％，将组成为Al2O3∶P2O5＝1∶1～3的磷酸铝胶体按照P2O5∶沸石(干基)＝1∶5～99的重量比与该沸石混合均匀，于300～600℃、10～100％水蒸汽下焙烧0.5～6小时。
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