CN111054328B - 一种烷基化原料选择加氢催化剂及其制备方法 - Google Patents
一种烷基化原料选择加氢催化剂及其制备方法 Download PDFInfo
- Publication number
- CN111054328B CN111054328B CN201811202638.8A CN201811202638A CN111054328B CN 111054328 B CN111054328 B CN 111054328B CN 201811202638 A CN201811202638 A CN 201811202638A CN 111054328 B CN111054328 B CN 111054328B
- Authority
- CN
- China
- Prior art keywords
- sepiolite
- catalyst
- roasting
- selective hydrogenation
- hydrogenation catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 112
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 46
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 28
- 230000029936 alkylation Effects 0.000 title claims abstract description 27
- 239000002994 raw material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004113 Sepiolite Substances 0.000 claims abstract description 85
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 85
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 85
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002791 soaking Methods 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 17
- 101150003085 Pdcl gene Proteins 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 13
- 230000004048 modification Effects 0.000 claims abstract description 11
- 238000012986 modification Methods 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims description 18
- 239000010410 layer Substances 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 239000002344 surface layer Substances 0.000 claims description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 abstract description 29
- 239000012752 auxiliary agent Substances 0.000 abstract description 20
- 238000006317 isomerization reaction Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 8
- 239000002893 slag Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 18
- 239000000292 calcium oxide Substances 0.000 description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 241000219782 Sesbania Species 0.000 description 7
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000001282 iso-butane Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- JVSWJIKNEAIKJW-UHFFFAOYSA-N 2-Methylheptane Chemical compound CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 244000146553 Ceiba pentandra Species 0.000 description 1
- 235000003301 Ceiba pentandra Nutrition 0.000 description 1
- 229910005084 FexOy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- 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
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- 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
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
- C07C5/05—Partial hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/13—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation with simultaneous isomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/44—Palladium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种烷基化原料选择加氢催化剂及其制备方法，属于加氢催化剂技术领域。其特征在于，组成包括Pd 0.2%~0.3%，二氧化钛1.0%~5.0，余为海泡石组分及助剂。制备步骤包括：取海泡石粉碎、浸泡，去除浮渣后过滤干燥；干燥后的海泡石中加入占海泡石质量4%~6%的偏钛酸粉并共同粉碎至粒径小于160目，焙烧改性6h~8h，焙烧温度为400℃~500℃，得到改性海泡石；将改性海泡石加入挤制成条，晾干，焙烧后得到催化剂载体；配制PdCl2溶液，与步骤3）得到的载体等体积浸渍，沥干后焙烧得到成品催化剂。该选择加氢催化剂具有同贵金属催化剂相当的催化活性，成本低、还具有很高的1‑丁烯异构化活性。
Description
技术领域
一种烷基化原料选择加氢催化剂及其制备方法，属于加氢催化剂技术领域。
背景技术
烷基化是现代炼油工业中生产高辛烷值汽油的重要加工过程。在硫酸或氢氟酸催化剂的作用下，异丁烷和烃反应生成的烷基化油是异构烷烃的混合物，其辛烷值高，敏感性小，而且具有理想的挥发性和清洁的燃烧性，是优质的高辛烷值汽油的理想调合组分。
烷基化原料是来自蒸汽裂解、催化裂化过程的混合碳四，其中的丁二烯含量一般为0.2%~2.0%(v/v)。丁二烯在烷基化反应中，可生成重质迭合物ASO。ASO是一种分子量很高的粘稠重质油，可使烷基化油的干点升高，辛烷值下降。同时，在酸再生塔分离这部分ASO时，也要损失部分酸，丁二烯含量越高，酸耗量越大。
对烷基化原料进行选择性加氢，可以有效的减少丁二烯含量，降低酸耗。另外，催化剂还能够使丁烯-1异构化为丁烯-2，而丁烯-2与异丁烷生成的三甲基戊烷，其辛烷值要比丁烯-1与异丁烷生成的二甲基已烷高3个单位，从而提高烷基化油质量，对环境保护具有重要意义。通常采用负载型Pd催化剂，以及液相固定床加氢工艺对烷基化原料进行预处理。
CN1238239提供了一种烷基化原料预处理方法，其采用了δ、θ、α混相氧化铝为载体，制备了负载型Pd催化剂，以提高催化剂活性及选择性，但并未示出该催化剂是否具有1-丁烯异构化性能。CN1621396提供了一种烷基化原料预处理方法，采用了具有超强顺磁性载体负载的Pd催化剂及流化床加氢工艺，虽然具有丁二烯加氢活性高、丁烯损失率低的优点，但未示出该催化剂是否具有1-丁烯异构化性能。CN101850250采用载体表面镁铝尖晶石改性及引入助剂Pb的方法，提高Pd催化剂的寿命，但也未提及该催化剂是否具有1-丁烯异构化性能。CN103418379采用以氧化钙改性的载体及引入WO3作为助剂的方法，提高Pd催化剂的单烯烃收率和抗硫性，也未提及该催化剂是否具有1-丁烯异构化性能。CN1676214 在氧化铝负载的 Pd 催化剂基础上，引入了两种助剂 X1和X 2，X1选自 B、P、Si 中的一种或多种，X2选自 K、Na、Li、Mg、Sr 中的一种或多种，并提供了一种烷基化原料的预处理方法，丁二烯加氢率99%以上，1- 丁烯异构化率可达 70%。现有烷基化原料预处理技术方案均采用负载型贵金属催化剂，因贵金属价格昂贵，存在催化剂成本较高的不足。
海泡石是一种富镁硅酸盐粘土矿物。其理论化学式为Mg8[Si2O30](OH)4·12H2O，水分子中有4个为结晶水：其余为沸石水。海泡石属于S单斜晶系或斜方晶系的链层状含水镁铝硅酸盐或镁硅酸盐矿物，其具有巨大的比表面积可吸附各类反应物及催化剂的活性组分，由于海泡石具有碱性和酸性中心，反应物易在中心极化为活化络合物，与催化剂产生协同催化作用。通过改性，海泡石孔径大小与反应物分子大小和催化剂组分大小相匹配，海泡石载体可表现出活性高选择性好，耐热性抗毒性高。
其中效果较好的有TiO2柱撑海泡石为载体制备催化剂，所谓“柱撑”是指通过柱化剂将金属氧化物（TiO2）撑进具有层状结构的海泡石层间，改变层间距，进而显著增加海泡石载体的比表面积和比孔容，有利于活性组分的吸附和分散，还能增加海泡石的饱和吸附量。但是该柱撑改性海泡石工艺复杂，制备周期长，不利于工业应用实施。
发明内容
本发明要解决的技术问题是：克服现有技术的不足，提供一种催化剂成本低、制备方便、1-丁烯异构化活性高的烷基化原料选择加氢催化剂及其制备方法。
本发明解决其技术问题所采用的技术方案是：该烷基化原料选择加氢催化剂，其特征在于以质量计，组成包括Pd 0.2%~0.3%，二氧化钛1.0%~5.0，余为海泡石组分及助剂。
本发明的加氢催化剂采用海泡石作为载体，添加钛进行热改性，负载Pd作为活性组分，具有同贵金属催化剂相当的催化活性，还具有很高的1-丁烯异构化活性。
优选的，以质量百分比计，组成包括Pd 0.23%~0.28%，二氧化钛2.0%~2.5%。优选的组成能够达到本催化剂的最佳效果。
优选的，催化剂的孔容为0.35mL/g ~0.40 mL/g，孔径90%为12nm~20nm，比表面积为150m2/g~180m2/g；堆积密度为0.75Kg/L ~0.80Kg/L，催化剂侧压强度为180 N/cm ~250N/cm，Pd粒径为8 nm~10nm。
优选的，催化剂的活性组分为催化剂表层的Pd层，Pd层厚度为310μm ~320μm。
本催化剂的物理性质能够充分的保证催化剂的催化效率。
一种所述烷基化原料选择加氢催化剂的制备方法，其特征在于，制备步骤包括：
1）取海泡石粉碎、浸泡，去除浮渣后过滤干燥；
2）干燥后的海泡石中加入占海泡石质量4%~6%的偏钛酸粉并共同粉碎至粒径小于160目，焙烧改性6h~8h，焙烧温度为400℃~500℃，得到改性海泡石；
3）将改性海泡石加入挤制成条，晾干，焙烧后得到催化剂载体；
4） 配制PdCl2溶液，与步骤3）得到的载体等体积浸渍，沥干后焙烧得到成品催化剂。
本发明通过对天然海泡石进行改性，负载Pd作为活性组分，热改性过程中加入的偏钛酸分解后的TiO2与活性组分Pd强相互作用SMSI（Strong Metal SupportInteraction），制备出一种烷基化原料选择加氢催化剂。
所述的海泡石为纤维状海泡石。颜色为白色或浅灰色，避免浅红、淡黄或褐色等。优选的，所述的海泡石为洁白色海泡石或灰白色海泡石；所述洁白色海泡石的质量百分比组成为：SiO266%~68%，MgO30%~32%，FexOy＜0.2%，余量为Al2O3、CaO；所述灰白色海泡石的质量百分比组成为：SiO265%~67%，MgO30%~32%，FexOy＜1.0%，余量为Al2O3、CaO。优选的海泡石更适合本发明的改性方式，更有利于本发明负载方法活性组分的吸附和分散。
优选的，步骤2）中所述焙烧温度为420℃~450℃。
优选的，步骤3）中所述的催化剂载体焙烧温度为430℃~460℃。温度过低则载体强度不够，温度过高则会破坏海泡石层状结构。
优选的，步骤4）中加入稀盐酸调节浸渍体系的pH值至2~2.3，浸渍时间为12 min ~15min。优选的浸渍反应条件，活性组分吸附更稳定，分散更均匀，催化效果更好。
优选的，步骤4）中所述焙烧的焙烧温度为380~450℃，焙烧时间为7.8 h ~8.2h。焙烧温度更优选为400~420℃；温度高低决定所期望的Pd的晶粒大小，另外温度过高会破坏海泡石载体的层状结构。
步骤4）中，PdCl2溶液浓度根据载体吸水率控制成品催化剂Pd含量为0.2~0.3wt%。
所述的挤制成条中还加入助剂，助剂为常规的造孔剂、助挤剂，包括但不限于硝酸、柠檬酸、木棉、木质纤维素、石墨、田菁粉。
与现有技术相比，本发明的一种烷基化原料选择加氢催化剂及其制备方法所具有的有益效果是：本发明提供了一种烷基化原料选择加氢催化剂及其制备方法。该加氢催化剂采用海泡石作为载体，添加钛进行热改性，负载Pd作为活性组分。热改性过程加入的TiO2与活性组分Pd强相互作用SMSI（Strong Metal Support Interaction）使该选择加氢催化剂具有良好的催化活性，选择性，还具有很高的1-丁烯异构化活性。
具体实施方式
下面结合具体实施例对本发明做进一步说明，其中实施例1为最佳实施。
实施例1
1）取100g洁白色海泡石粉碎、浸泡，去除浮渣后过滤干燥；干燥后的海泡石加入5.5g偏钛酸粉碎至小于160目，435℃焙烧7h，得到改性海泡石A；其中洁白色海泡石的质量百分比组成为：SiO267%，MgO31%，FexOy＜0.2%，余量为Al2O3、CaO；
2）改性海泡石A加入3g助剂田菁粉挤制成条状，晾干，435℃焙烧8h得到催化剂载体B；
3）PdCl2加入稀HCl中配成PdCl2溶液，溶液PH值为2，与载体B等体积浸渍13min后沥干，400℃焙烧8h得到成品加氢催化剂H-1；
加氢催化剂H-1组成包括Pd 0.25%，二氧化钛2.5%，余为海泡石组分及助剂。催化剂的孔容为0.35mL/g ~0.40 mL/g，孔径90%为12nm~20nm，比表面积为180m2/g；堆积密度为0.80Kg/L，催化剂侧压强度为250N/cm，Pd粒径为8 nm~10nm；催化剂的Pd层厚度为320μm。
实施例2
1）取100g洁白色海泡石粉碎、浸泡，去除浮渣后过滤干燥；干燥后的海泡石加入4.5%偏钛酸粉碎至小于160目，420℃焙烧7.8h，得到改性海泡石A；其中洁白色海泡石的质量百分比组成为：SiO268%，MgO30%%，FexOy＜0.2%，余量为Al2O3、CaO；
2）改性海泡石A加入5g助剂田菁粉、5g木质纤维素混合挤制成条状，晾干，450℃焙烧8h得到催化剂载体B；
3）PdCl2加入稀HCl中配成PdCl2溶液，溶液PH值为2.1，与载体B等体积浸渍15min后沥干，420℃焙烧8h得到成品加氢催化剂H-2；
加氢催化剂H-1组成包括Pd 0.28%，二氧化钛2.0%，余为海泡石组分及助剂。催化剂的孔容为0.35mL/g ~0.40 mL/g，孔径90%为12nm~20nm，比表面积为176m2/g；堆积密度为0.79Kg/L，催化剂侧压强度为246N/cm，Pd粒径为8 nm~10nm；催化剂的Pd层厚度为318μm。
实施例3
1）取100g洁白色海泡石粉碎、浸泡，去除浮渣后过滤干燥；干燥后的海泡石加入5%偏钛酸粉碎至小于160目， 450℃焙烧6.3h，得到改性海泡石A；其中洁白色海泡石的质量百分比组成为：SiO266%，MgO2%，FexOy＜0.2%，余量为Al2O3、CaO；
2）改性海泡石A加入5g助剂田菁粉挤制成条状，晾干，460℃焙烧8h得到催化剂载体B；
3）PdCl2加入稀HCl中配成PdCl2溶液，溶液PH值为2.3，与载体B等体积浸渍15min后沥干，400℃焙烧8h得到成品加氢催化剂H-3；
加氢催化剂H-1组成包括Pd 0.23%，二氧化钛2.3%，余为海泡石组分及助剂。催化剂的孔容为0.35mL/g ~0.40 mL/g，孔径90%为12nm~20nm，比表面积为178m2/g；堆积密度为0.78Kg/L，催化剂侧压强度为243N/cm，Pd粒径为8 nm~10nm；催化剂的Pd层厚度为319μm。
实施例4
1）取100g灰白色海泡石粉碎、浸泡，去除浮渣后过滤干燥；干燥后的海泡石加入6%偏钛酸粉碎至小于160目， 500℃焙烧6 h，得到改性海泡石A；其中灰白色海泡石的质量百分比组成为：SiO265%，MgO32%，FexOy＜1.0%，余量为Al2O3、CaO；
2）改性海泡石A加入3g助剂田菁粉挤制成条状，晾干，430℃焙烧8h得到催化剂载体B；
3）PdCl2加入稀HCl中配成PdCl2溶液，溶液PH值为2，与载体B等体积浸渍13min后沥干，420℃焙烧8h得到成品加氢催化剂H-4；
加氢催化剂H-1组成包括Pd 0.2%，二氧化钛5.0%，余为海泡石组分及助剂。催化剂的孔容为0.35mL/g ~0.40 mL/g，孔径90%为12nm~20nm，比表面积为168m2/g；堆积密度为0.77Kg/L，催化剂侧压强度为232N/cm，Pd粒径为8 nm~10nm；催化剂的Pd层厚度为316μm。
实施例5
1）取100g灰白色海泡石粉碎、浸泡，去除浮渣后过滤干燥；干燥后的海泡石加入4%偏钛酸粉碎至小于160目， 400℃焙烧8h，得到改性海泡石A；其中灰白色海泡石的质量百分比组成为：SiO267%，MgO30%，FexOy＜1.0%，余量为Al2O3、CaO；
2）改性海泡石A加入3g助剂田菁粉挤制成条状，晾干，430℃焙烧8h得到催化剂载体B；
3）PdCl2加入稀HCl中配成PdCl2溶液，溶液PH值为2，与载体B等体积浸渍14min后沥干，410℃焙烧8h得到成品加氢催化剂H-5；
加氢催化剂H-1组成包括Pd 0.3%，二氧化钛1.8%，余为海泡石组分及助剂。催化剂的孔容为0.35mL/g ~0.40 mL/g，孔径90%为12nm~20nm，比表面积为171m2/g；堆积密度为0.78Kg/L，催化剂侧压强度为228N/cm，Pd粒径为8 nm~10nm；催化剂的Pd层厚度为315μm。
实施例6
1）取100g浅灰色海泡石粉碎、浸泡，去除浮渣后过滤干燥；干燥后的海泡石加入5.5g偏钛酸粉碎至小于160目，420℃焙烧8h，得到改性海泡石A；
2）改性海泡石A加入3g助剂田菁粉挤制成条状，晾干，480℃焙烧8h得到催化剂载体B；
3）PdCl2加入稀HCl中配成PdCl2溶液，溶液PH值为2，与载体B等体积浸渍13min后沥干，450℃焙烧8h得到成品加氢催化剂H-6；
加氢催化剂H-1组成包括Pd 0.2%，二氧化钛1.0%，余为海泡石组分及助剂。催化剂的孔容为0.35mL/g ~0.40 mL/g，孔径90%为12nm~20nm，比表面积为150m2/g；堆积密度为0.75Kg/L，催化剂侧压强度为180 N/cm，Pd粒径为8 nm~10nm；催化剂的Pd层厚度为310μm。
本发明中，采用丁二烯加氢率、丁烯收率和1-丁烯异构化率来代表催化剂的反应性能。前两个指标用来表示催化剂的选择性加氢性能、第三个指标用来表示催化剂的异构化性能。丁二烯加氢率、丁烯损失率和1-丁烯异构率的计算方法如下：
催化剂评价条件：反应温度60℃，反应压力1.5MPa，液空速10h-1，氢气/丁二烯摩尔比1.5。
评价所用的C4原料组成见表1。实施例制备的催化剂及对比催化剂的评价数据列于表2。
表2 各选择加氢催化剂的评价数据
以上所述，仅是本发明的较佳实施例而已，并非是对本发明作其它形式的限制，任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更或改型为等同变化的等效实施例。但是凡是未脱离本发明技术方案内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与改型，仍属于本发明技术方案的保护范围。
Claims (9)
1.一种烷基化原料选择加氢催化剂，其特征在于以质量计，组成包括Pd 0.2%~0.3%，二氧化钛1.0%~5.0，余为海泡石组分及助剂；
其制备方法包括以下步骤：
1）取海泡石粉碎、浸泡，去除浮渣后过滤干燥；
2）干燥后的海泡石中加入占海泡石质量4%~6%的偏钛酸粉并共同粉碎至粒径小于160目，焙烧改性6h~8h，焙烧温度为400℃~500℃，得到改性海泡石；
3）将改性海泡石加入挤制成条，晾干，焙烧后得到催化剂载体；
4） 配制PdCl2溶液，与步骤3）得到的载体等体积浸渍，沥干后焙烧得到成品催化剂。
2.根据权利要求1所述的一种烷基化原料选择加氢催化剂，其特征在于：以质量百分比计，组成包括Pd 0.23%~0.28%，二氧化钛2.0%~2.5%。
3.根据权利要求1所述的一种烷基化原料选择加氢催化剂，其特征在于：催化剂的孔容为0.35mL/g ~0.40 mL/g，孔径90%为12nm~20nm，比表面积为150m2/g~180m2/g；堆积密度为0.75Kg/L ~0.80Kg/L，催化剂侧压强度为180 N/cm ~250N/cm，Pd粒径为8 nm~10nm。
4.根据权利要求1所述的一种烷基化原料选择加氢催化剂，其特征在于：催化剂的活性组分为催化剂表层的Pd层，Pd层厚度为310μm ~320μm。
5.根据权利要求1所述的一种烷基化原料选择加氢催化剂，其特征在于：所述的海泡石为洁白色海泡石或灰白色海泡石；所述洁白色海泡石的质量百分比组成为：SiO266%~68%，MgO30%~32%，FexOy＜0.2%，余量为Al2O3、CaO；所述灰白色海泡石的质量百分比组成为：SiO265%~67%，MgO30%~32%，FexOy＜1.0%，余量为Al2O3、CaO。
6.根据权利要求1所述的一种烷基化原料选择加氢催化剂，其特征在于：步骤2）中所述焙烧温度为420℃~450℃。
7.根据权利要求1所述的一种烷基化原料选择加氢催化剂，其特征在于：步骤3）中所述的催化剂载体焙烧温度为430℃~460℃。
8.根据权利要求1所述的一种烷基化原料选择加氢催化剂，其特征在于：步骤4）中加入稀盐酸调节浸渍体系的pH值至2~2.3，浸渍时间为12 min ~15min。
9.根据权利要求1所述的一种烷基化原料选择加氢催化剂，其特征在于：步骤4）中所述焙烧的焙烧温度为380~450℃，焙烧时间为7.8 h ~8.2h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811202638.8A CN111054328B (zh) | 2018-10-16 | 2018-10-16 | 一种烷基化原料选择加氢催化剂及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811202638.8A CN111054328B (zh) | 2018-10-16 | 2018-10-16 | 一种烷基化原料选择加氢催化剂及其制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111054328A CN111054328A (zh) | 2020-04-24 |
| CN111054328B true CN111054328B (zh) | 2023-04-11 |
Family
ID=70296550
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811202638.8A Active CN111054328B (zh) | 2018-10-16 | 2018-10-16 | 一种烷基化原料选择加氢催化剂及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111054328B (zh) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1161071A (en) * | 1965-07-16 | 1969-08-13 | Union Carbide Corp | Catalyst Composition |
| CN1548368A (zh) * | 2003-05-13 | 2004-11-24 | 中国科学院生态环境研究中心 | 富氢条件下一氧化碳选择性氧化催化剂 |
| CN1640541A (zh) * | 2004-01-12 | 2005-07-20 | 四川大学 | 一种炔烃选择加氢用以二氧化钛为载体的担载钯催化剂 |
| CN107721843A (zh) * | 2017-10-30 | 2018-02-23 | 中国成达工程有限公司 | 一种用乙炔双羰基化产物催化加氢合成丁二酸的方法 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050070740A1 (en) * | 2003-09-29 | 2005-03-31 | Rode Chandrashekhar Vasant | Nickel catalyst, process for the preparation thereof, process for hydrogenation of m-dinitro benzene to m-phenylene diamine |
-
2018
- 2018-10-16 CN CN201811202638.8A patent/CN111054328B/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1161071A (en) * | 1965-07-16 | 1969-08-13 | Union Carbide Corp | Catalyst Composition |
| CN1548368A (zh) * | 2003-05-13 | 2004-11-24 | 中国科学院生态环境研究中心 | 富氢条件下一氧化碳选择性氧化催化剂 |
| CN1640541A (zh) * | 2004-01-12 | 2005-07-20 | 四川大学 | 一种炔烃选择加氢用以二氧化钛为载体的担载钯催化剂 |
| CN107721843A (zh) * | 2017-10-30 | 2018-02-23 | 中国成达工程有限公司 | 一种用乙炔双羰基化产物催化加氢合成丁二酸的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111054328A (zh) | 2020-04-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20140323785A1 (en) | Catalyst composite for dehydrogenation of hydrocarbons and method of preparation thereof | |
| GB2076793A (en) | Cesium-or thallium-containing zeolite and its preparation | |
| RU2654205C1 (ru) | Подложка для способа селективного синтеза высококачественной керосиновой фракции из синтез-газа, катализатор этого способа и способ их изготовления | |
| US10773249B2 (en) | Preparation of a ZSM-5-based catalyst; use in ethylbenzene dealkylation process | |
| JPH0685875B2 (ja) | 炭化水素油の接触分解用触媒と接触分解法 | |
| US3669903A (en) | Catalytic cracking process | |
| CN102233282B (zh) | 一种以氧化硅-氧化铝为载体的费托合成催化剂及其应用 | |
| CN113289673B (zh) | 一种异构化催化剂及其制备方法和应用 | |
| CN104588008B (zh) | 饱和烷烃脱氢催化剂及其制备方法 | |
| KR20190059283A (ko) | 알킬방향족 전환 촉매 | |
| US3370099A (en) | Isomerization process | |
| CN111054328B (zh) | 一种烷基化原料选择加氢催化剂及其制备方法 | |
| CN101172248B (zh) | 一种c7～c20烷烃异构化催化剂及异构化方法 | |
| US3598724A (en) | Production of propane and butanes | |
| CN111054364B (zh) | 一种镍系烷基化原料选择加氢催化剂及其制备方法 | |
| CN1501841A (zh) | 具有超高动力学转化活性的基于沸石的催化剂 | |
| RU2287370C1 (ru) | Способ получения шарикового катализатора крекинга | |
| US3533939A (en) | Reforming with a crystalline aluminosilicate free of hydrogenation activity | |
| RU2458103C1 (ru) | Носитель катализатора для риформинга бензиновых фракций и способ его приготовления | |
| KR20200066436A (ko) | 니켈계 올리고머화 촉매 및 이를 이용하여 경질 올레핀을 올리고머화하는 방법 | |
| CN112275309B (zh) | 烷烃异构化催化剂载体、载体制备方法及其所得催化剂 | |
| JP4541688B2 (ja) | イソパラフィン−オレフィンアルキル化法 | |
| JP3068347B2 (ja) | 高オクタン価ガソリン基材の製造方法 | |
| WO2020151646A1 (zh) | 固体酸催化剂、其制备和应用 | |
| RU2430955C1 (ru) | Способ получения моторных топлив |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |