公开(公告)号：US09968915B2

公开(公告)日：2018-05-15

申请号：US14404774

申请日：2012-07-27

申请人： Xionghou Gao ,  Haitao Zhang ,  Di Li ,  Xueli Li ,  Hongchang Duan ,  Zhengguo Tan ,  Chaowei Liu ,  Yunfeng Zheng ,  Xiaoliang Huang ,  Jinjun Cai ,  Chenxi Zhang ,  Zhishuang Pan ,  Gengzhen Cao

发明人： Xionghou Gao ,  Haitao Zhang ,  Di Li ,  Xueli Li ,  Hongchang Duan ,  Zhengguo Tan ,  Chaowei Liu ,  Yunfeng Zheng ,  Xiaoliang Huang ,  Jinjun Cai ,  Chenxi Zhang ,  Zhishuang Pan ,  Gengzhen Cao

IPC分类号： B01J29/06 ,  B01J29/08 ,  B01J29/80 ,  B01J37/30 ,  B01J35/10 ,  C01B39/02 ,  B01J37/28 ,  C01B39/24 ,  C01B39/54 ,  B01J37/00 ,  B01J37/04 ,  B01J37/06 ,  B01J37/08

CPC分类号： B01J29/088 ,  B01J29/084 ,  B01J29/80 ,  B01J35/10 ,  B01J35/109 ,  B01J37/009 ,  B01J37/04 ,  B01J37/06 ,  B01J37/08 ,  B01J37/28 ,  B01J37/30 ,  B01J2229/18 ,  B01J2229/186 ,  B01J2229/40 ,  B01J2229/42 ,  C01B39/026 ,  C01B39/24 ,  C01B39/54

摘要： Provided is a phosphorus-containing ultrastable Y-type rare earth (RE) molecular sieve and the preparation method thereof. The method is: based on NaY molecular sieve as a raw material, obtaining “one-exchange one-roast” RE-Na Y-type molecular sieve through the steps of exchanging with RE, pre-exchanging with dispersing, and the first calcination; and then performing ammonium salt exchange, phosphorus modification, and the second calcination on the “one-exchange one-roast” RE-Na Y-type molecular sieve, wherein the sequence of the RE exchange and the pre-exchange with dispersing is unlimited, and the sequence of the ammonium salt exchange and the phosphorus modification is unlimited as well. The obtained molecular sieve contains RE oxide 1-20 wt %, phosphorus 0.1-5 wt %, and sodium oxide no more than 1.2 wt %, and has a crystallization degree of 51-69% and a lattice parameter of 2.449-2.469 nm. Heavy oil conversion rate can be increased by using the molecular sieve as an active component in a catalytic cracking catalyst.

公开(公告)号：US20150165428A1

公开(公告)日：2015-06-18

申请号：US14404776

申请日：2012-07-27

申请人： Xionghou Gao ,  Haitao Zhang ,  Di Li ,  Zhengguo Tan ,  Hongchang Duan ,  Xueli Li ,  Chaowei Liu ,  Yunfeng Zheng ,  Xiaoliang Huang ,  Jinjun Cai ,  Zhishuang Pan ,  Xueqin Sun

发明人： Xionghou Gao ,  Haitao Zhang ,  Di Li ,  Zhengguo Tan ,  Hongchang Duan ,  Xueli Li ,  Chaowei Liu ,  Yunfeng Zheng ,  Xiaoliang Huang ,  Jinjun Cai ,  Zhishuang Pan ,  Xueqin Sun

IPC分类号： B01J29/85 ,  B01J37/08 ,  B01J37/30 ,  B01J37/04 ,  B01J21/16 ,  B01J29/70 ,  B01J29/80 ,  B01J37/06

CPC分类号： B01J29/85 ,  B01J21/16 ,  B01J29/084 ,  B01J29/088 ,  B01J29/40 ,  B01J29/605 ,  B01J29/7003 ,  B01J29/7007 ,  B01J29/7049 ,  B01J29/80 ,  B01J35/002 ,  B01J35/10 ,  B01J35/109 ,  B01J37/0018 ,  B01J37/0045 ,  B01J37/04 ,  B01J37/06 ,  B01J37/08 ,  B01J37/28 ,  B01J37/30 ,  B01J2229/18 ,  B01J2229/186 ,  B01J2229/36 ,  B01J2229/37 ,  B01J2229/40 ,  B01J2229/42 ,  C01B39/026 ,  C01B39/24 ,  C10G11/05 ,  C10G2400/30

摘要： The present invention provides a catalytic cracking catalyst for heavy oil and preparation methods thereof. The catalyst comprises 2 to 50% by weight of a phosphorus-containing ultrastable rare earth Y-type molecular sieve, 0.5 to 30% by weight of one or more other molecular sieves, 0.5 to 70% by weight of clay, 1.0 to 65% by weight of high-temperature-resistant inorganic oxides, and 0.01 to 12.5% by weight of a rare earth oxide. The phosphorus-containing ultra-stable rare earth Y-type molecular sieve uses a NaY molecular sieve as a raw material. The raw material is subjected to a rare-earth exchange and a dispersing pre-exchange; the molecular sieve slurry is then filtered, washed with water and subjected to a first calcination to obtain a rare earth sodium Y molecular sieve which has been subjected to such “first-exchange first-calcination”, wherein the steps of rare earth exchange and dispersing pre-exchange are not restricted in sequence; and then the rare earth sodium Y molecular sieve which has been subjected to “one-exchange one-calcination” is subjected to “second exchange and second calcination” including ammonium exchange and a phosphorus modification, wherein the steps of the ammonium exchange and the phosphorus modification are not restricted in sequence. The steps of the ammonium exchange and the phosphorus modification can be conducted continuously or non-continuously, the second calcination is conducted after the ammonium exchange for reducing sodium, the phosphorus modification can be conducted before or after the second calcination. The catalyst provided by the invention has the characteristics of high heavy oil conversion capacity, high total liquid yield, and high yield of light oil.

摘要翻译： 本发明提供一种重油催化裂化催化剂及其制备方法。 该催化剂含有2〜50重量％的含磷超纯稀土Y型分子筛，0.5〜30重量％的一种或多种其它分子筛，0.5〜70重量％的粘土，1.0〜65重量％ 的耐高温无机氧化物，0.01〜12.5重量％的稀土类氧化物。 含磷超稳定稀土Y型分子筛采用NaY分子筛为原料。 原料进行稀土交换和分散预交换; 然后将分子筛浆液过滤，用水洗涤并进行第一次煅烧，得到已经进行了这种“第一次交换第一次煅烧”的稀土钠Y分子筛，其中稀土交换和分散的步骤 预交换不受限制; 然后进行“一次一煅烧”的稀土钠Y分子筛进行铵交换和磷改性的“二次交换和二次煅烧”，其中铵交换和磷的步骤 修改不受限制。 铵交换和磷改性的步骤可以连续地或不连续地进行，第二次煅烧在铵还原钠进行之后进行，可以在第二次煅烧之前或之后进行磷改性。 本发明提供的催化剂具有重油转化率高，总液体产率高，轻油产率高的特点。

公开(公告)号：US20150209767A1

公开(公告)日：2015-07-30

申请号：US14404774

申请日：2012-07-27

申请人： Xionghou Gao ,  Haitao Zhang ,  Di Li ,  Xueli Li ,  Hongchang Duan ,  Zhengguo Tan ,  Chaowei Liu ,  Yunfeng Zheng ,  Xiaoliang Huang ,  Jinjun Cai ,  Chenxi Zhang ,  Zhishuang Pan ,  Gengzhen Cao

发明人： Xionghou Gao ,  Haitao Zhang ,  Di Li ,  Xueli Li ,  Hongchang Duan ,  Zhengguo Tan ,  Chaowei Liu ,  Yunfeng Zheng ,  Xiaoliang Huang ,  Jinjun Cai ,  Chenxi Zhang ,  Zhishuang Pan ,  Gengzhen Cao

IPC分类号： B01J29/08 ,  B01J37/00 ,  B01J37/06 ,  B01J37/04 ,  C01B39/24 ,  B01J37/08

CPC分类号： B01J29/088 ,  B01J29/084 ,  B01J29/80 ,  B01J35/10 ,  B01J35/109 ,  B01J37/009 ,  B01J37/04 ,  B01J37/06 ,  B01J37/08 ,  B01J37/28 ,  B01J37/30 ,  B01J2229/18 ,  B01J2229/186 ,  B01J2229/40 ,  B01J2229/42 ,  C01B39/026 ,  C01B39/24 ,  C01B39/54

摘要： Provided is a phosphorus-containing ultrastable Y-type rare earth (RE) molecular sieve and the preparation method thereof. The method is: based on Na Y molecular sieve as a raw material, obtaining “one-exchange one-roast” RE-Na Y-type molecular sieve through the steps of exchanging with RE, pre-exchanging with dispersing, and the first calcination; and then performing ammonium salt exchange, phosphorus modification, and the second calcination on the “one-exchange one-roast” RE-Na Y-type molecular sieve, wherein the sequence of the RE exchange and the pre-exchange with dispersing is unlimited, and the sequence of the ammonium salt exchange and the phosphorus modification is unlimited as well. The obtained molecular sieve contains RE oxide 1-20 wt %, phosphorus 0.1-5 wt %, and sodium oxide no more than 1.2 wt %, and has a crystallization degree of 51-69% and a lattice parameter of 2.449-2.469 nm. Heavy oil conversion rate can be increased by using the molecular sieve as an active component in a catalytic cracking catalyst.

摘要翻译： 提供一种含磷超纯Y型稀土（RE）分子筛及其制备方法。 方法为：以Na Y分子筛为原料，通过与RE交换，分散预交换和第一次煅烧的步骤获得“一换一烘焙”RE-Na Y型分子筛 ; 然后在“一换一烘焙”RE-Na Y型分子筛上进行铵盐交换，磷改性和第二次煅烧，其中RE交换和分散预交换的顺序是无限的， 并且铵盐交换和磷改性的顺序也是无限的。 得到的分子筛含有1-20重量％的RE氧化物，0.1-5重量％的磷，不超过1.2重量％的氧化钠，结晶度为51-69％，晶格参数为2.449-2.469nm。 通过在催化裂化催化剂中使用分子筛作为活性组分可以提高重油转化率。

公开(公告)号：US09889439B2

公开(公告)日：2018-02-13

申请号：US14364652

申请日：2012-04-13

申请人： Xionghou Gao ,  Haitao Zhang ,  Hongchang Duan ,  Di Li ,  Xueli Li ,  Zhengguo Tan ,  Xiaoliang Huang ,  Jinjun Cai ,  Yunfeng Zheng ,  Chenxi Zhang ,  Gengzhen Cao

发明人： Xionghou Gao ,  Haitao Zhang ,  Hongchang Duan ,  Di Li ,  Xueli Li ,  Zhengguo Tan ,  Xiaoliang Huang ,  Jinjun Cai ,  Yunfeng Zheng ,  Chenxi Zhang ,  Gengzhen Cao

IPC分类号： B01J29/06 ,  B01J29/80 ,  B01J35/10 ,  B01J29/84 ,  B01J37/30 ,  C01B39/24 ,  B01J29/08 ,  C01B39/02 ,  C10G11/18

CPC分类号： B01J29/80 ,  B01J29/088 ,  B01J29/84 ,  B01J35/10 ,  B01J35/109 ,  B01J37/30 ,  B01J2029/062 ,  B01J2229/186 ,  B01J2229/40 ,  B01J2229/42 ,  C01B39/026 ,  C01B39/24 ,  C10G11/18

摘要： The present invention relates to a heavy oil catalytic cracking catalyst having a high yield of light oil and preparation methods thereof. The catalyst comprises 2 to 50% by weight of a magnesium-modified ultra-stable rare earth type Y molecular sieve, 0.5 to 30% by weight of one or more other molecular sieves, 0.5 to 70% by weight of clay, 1.0 to 65% by weight of high-temperature-resistant inorganic oxides, and 0.01 to 12.5% by weight of rare earth oxide. The magnesium-modified ultra-stable rare earth type Y molecular sieve is obtained by the following manner: the raw material, a NaY molecular sieve, is subjected to a rare earth exchange, a dispersing pre-exchange, a magnesium salt exchange modification, an ammonium salt exchange for sodium reduction, a second exchange and a second calcination. The catalyst provided in the present invention is characteristic in its high conversion capacity of heavy oil and a high yield of light oil.

公开(公告)号：US09840422B2

公开(公告)日：2017-12-12

申请号：US14365432

申请日：2012-04-13

申请人： Xionghou Gao ,  Haitao Zhang ,  Hongchang Duan ,  Chaowei Liu ,  Di Li ,  Xueli Li ,  Zhengguo Tan ,  Yunfeng Zheng ,  Xiaoliang Huang ,  Jinjun Cai ,  Chenxi Zhang

发明人： Xionghou Gao ,  Haitao Zhang ,  Hongchang Duan ,  Chaowei Liu ,  Di Li ,  Xueli Li ,  Zhengguo Tan ,  Yunfeng Zheng ,  Xiaoliang Huang ,  Jinjun Cai ,  Chenxi Zhang

IPC分类号： B01J29/06 ,  C01B39/24 ,  B01J29/08 ,  B01J29/80 ,  B01J35/10 ,  C10G11/05 ,  B01J35/02 ,  C01B39/02 ,  B01J37/08 ,  B01J37/30

CPC分类号： C01B39/24 ,  B01J29/084 ,  B01J29/088 ,  B01J29/80 ,  B01J35/023 ,  B01J35/10 ,  B01J35/109 ,  B01J37/08 ,  B01J37/30 ,  B01J2229/18 ,  B01J2229/186 ,  B01J2229/40 ,  B01J2229/42 ,  C01B39/026 ,  C10G11/05

摘要： The present invention provides a magnesium-modified ultra-stable rare earth type Y molecular sieve and the preparation method thereof, which method is carried out by subjecting a NaY molecular sieve as the raw material to a rare earth exchange and a dispersing pre-exchange, then to an ultra-stabilization calcination treatment, and finally to a magnesium modification. The molecular sieve comprises 0.2 to 5% by weight of magnesium oxide, 1 to 20% by weight of rare earth oxide, and not more than 1.2% by weight of sodium oxide, and has a crystallinity of 46 to 63%, and a lattice parameter of 2.454 nm to 2.471 nm. In contrast to the prior art, in the molecular sieve prepared by this method, rare earth ions are located in sodalite cages, which is demonstrated by the fact that no rare earth ion is lost during the reverse exchange process. Moreover, the molecular sieve prepared by such a method has a molecular particle size D(v,0.5) of not more than 3.0 μm and a D(v,0.9) of not more than 20 μm. Such a molecular sieve has both high stability and high selectivity for the target product, while cracking catalysts using the molecular sieve as an active component is characterized by a high heavy-oil-conversion capacity and a high yield of valuable target products.

公开(公告)号：US09968918B2

公开(公告)日：2018-05-15

申请号：US14404776

申请日：2012-07-27

申请人： Xionghou Gao ,  Haitao Zhang ,  Di Li ,  Zhengguo Tan ,  Hongchang Duan ,  Xueli Li ,  Chaowei Liu ,  Yunfeng Zheng ,  Xiaoliang Huang ,  Jinjun Cai ,  Zhishuang Pan ,  Xueqin Sun

发明人： Xionghou Gao ,  Haitao Zhang ,  Di Li ,  Zhengguo Tan ,  Hongchang Duan ,  Xueli Li ,  Chaowei Liu ,  Yunfeng Zheng ,  Xiaoliang Huang ,  Jinjun Cai ,  Zhishuang Pan ,  Xueqin Sun

IPC分类号： B01J29/06 ,  B01J29/85 ,  C01B39/24 ,  C01B39/02 ,  B01J35/10 ,  C10G11/05 ,  B01J37/28 ,  B01J29/08 ,  B01J29/40 ,  B01J21/16 ,  B01J29/70 ,  B01J29/80 ,  B01J37/06 ,  B01J37/08 ,  B01J37/30 ,  B01J35/00 ,  B01J37/00 ,  B01J29/60 ,  B01J37/04

CPC分类号： B01J29/85 ,  B01J21/16 ,  B01J29/084 ,  B01J29/088 ,  B01J29/40 ,  B01J29/605 ,  B01J29/7003 ,  B01J29/7007 ,  B01J29/7049 ,  B01J29/80 ,  B01J35/002 ,  B01J35/10 ,  B01J35/109 ,  B01J37/0018 ,  B01J37/0045 ,  B01J37/04 ,  B01J37/06 ,  B01J37/08 ,  B01J37/28 ,  B01J37/30 ,  B01J2229/18 ,  B01J2229/186 ,  B01J2229/36 ,  B01J2229/37 ,  B01J2229/40 ,  B01J2229/42 ,  C01B39/026 ,  C01B39/24 ,  C10G11/05 ,  C10G2400/30

摘要： The present invention provides a catalytic cracking catalyst for heavy oil and preparation methods thereof. The catalyst comprises 2 to 50% by weight of a phosphorus-containing ultrastable rare earth Y-type molecular sieve, 0.5 to 30% by weight of one or more other molecular sieves, 0.5 to 70% by weight of clay, 1.0 to 65% by weight of high-temperature-resistant inorganic oxides, and 0.01 to 12.5% by weight of a rare earth oxide. The phosphorus-containing ultra-stable rare earth Y-type molecular sieve uses a NaY molecular sieve as a raw material. The raw material is subjected to a rare-earth exchange and a dispersing pre-exchange; the molecular sieve slurry is then filtered, washed with water and subjected to a first calcination to obtain a rare earth sodium Y molecular sieve which has been subjected to such “first-exchange first-calcination”, wherein the steps of rare earth exchange and dispersing pre-exchange are not restricted in sequence; and then the rare earth sodium Y molecular sieve which has been subjected to “one-exchange one-calcination” is subjected to “second exchange and second calcination” including ammonium exchange and a phosphorus modification, wherein the steps of the ammonium exchange and the phosphorus modification are not restricted in sequence. The steps of the ammonium exchange and the phosphorus modification can be conducted continuously or non-continuously, the second calcination is conducted after the ammonium exchange for reducing sodium, the phosphorus modification can be conducted before or after the second calcination. The catalyst provided by the invention has the characteristics of high heavy oil conversion capacity, high total liquid yield, and high yield of light oil.

公开(公告)号：US20150175432A1

公开(公告)日：2015-06-25

申请号：US14365432

申请日：2012-04-13

申请人： Xionghou Gao ,  Haitao Zhang ,  Hongchang Duan ,  Chaowei Liu ,  Di Li ,  Xueli Li ,  Zhengguo Tan ,  Yunfeng Zheng ,  Xiaoliang Huang ,  Jinjun Cai ,  Chenxi Zhang

发明人： Xionghou Gao ,  Haitao Zhang ,  Hongchang Duan ,  Chaowei Liu ,  Di Li ,  Xueli Li ,  Zhengguo Tan ,  Yunfeng Zheng ,  Xiaoliang Huang ,  Jinjun Cai ,  Chenxi Zhang

IPC分类号： C01B39/24 ,  B01J29/08 ,  B01J37/08 ,  C01B39/02

CPC分类号： C01B39/24 ,  B01J29/084 ,  B01J29/088 ,  B01J29/80 ,  B01J35/023 ,  B01J35/10 ,  B01J35/109 ,  B01J37/08 ,  B01J37/30 ,  B01J2229/18 ,  B01J2229/186 ,  B01J2229/40 ,  B01J2229/42 ,  C01B39/026 ,  C10G11/05

摘要： The present invention provides a magnesium-modified ultra-stable rare earth type Y molecular sieve and the preparation method thereof, which method is carried out by subjecting a NaY molecular sieve as the raw material to a rare earth exchange and a dispersing pre-exchange, then to an ultra-stabilization calcination treatment, and finally to a magnesium modification. The molecular sieve comprises 0.2 to 5% by weight of magnesium oxide, 1 to 20% by weight of rare earth oxide, and not more than 1.2% by weight of sodium oxide, and has a crystallinity of 46 to 63%, and a lattice parameter of 2.454 nm to 2.471 nm. In contrast to the prior art, in the molecular sieve prepared by this method, rare earth ions are located in sodalite cages, which is demonstrated by the fact that no rare earth ion is lost during the reverse exchange process. Moreover, the molecular sieve prepared by such a method has a molecular particle size D(v,0.5) of not more than 3.0 μm and a D(v,0.9) of not more than 20 μm. Such a molecular sieve has both high stability and high selectivity for the target product, while cracking catalysts using the molecular sieve as an active component is characterized by a high heavy-oil-conversion capacity and a high yield of valuable target products.

摘要翻译： 本发明提供一种镁改性超稳定稀土类Y分子筛及其制备方法，该方法是以NaY分子筛为原料进行稀土交换和分散预交换， 然后进行超稳定化煅烧处理，最后进行镁改性。 分子筛含有0.2〜5重量％的氧化镁，1〜20重量％的稀土氧化物和1.2重量％的氧化钠，结晶度为46〜63％，晶格 参数为2.454 nm至2.471 nm。 与现有技术相反，在通过该方法制备的分子筛中，稀土离子位于钠盐网箱中，这通过在反向交换过程中没有稀土离子损失的事实来证明。 此外，通过这种方法制备的分子筛具有不大于3.0μm的分子粒度D（v，0.5）和不大于20μm的D（v，0.9）。 这种分子筛对于目标产物具有高稳定性和高选择性，而使用分子筛作为活性组分的裂化催化剂的特征在于高重油转化能力和高产率的有价值的目标产物。

公开(公告)号：US20150011378A1

公开(公告)日：2015-01-08

申请号：US14364652

申请日：2012-04-13

申请人： Xionghou Gao ,  Haitao Zhang ,  Hongchang Duan ,  Di Li ,  Xueli Li ,  Zhengguo Tan ,  Xiaoliang Huang ,  Jinjun Cai ,  Yunfeng Zheng ,  Chenxi Zhang ,  Gengzhen Cao

发明人： Xionghou Gao ,  Haitao Zhang ,  Hongchang Duan ,  Di Li ,  Xueli Li ,  Zhengguo Tan ,  Xiaoliang Huang ,  Jinjun Cai ,  Yunfeng Zheng ,  Chenxi Zhang ,  Gengzhen Cao

IPC分类号： B01J29/80

CPC分类号： B01J29/80 ,  B01J29/088 ,  B01J29/84 ,  B01J35/10 ,  B01J35/109 ,  B01J37/30 ,  B01J2029/062 ,  B01J2229/186 ,  B01J2229/40 ,  B01J2229/42 ,  C01B39/026 ,  C01B39/24 ,  C10G11/18

摘要： The present invention relates to a heavy oil catalytic cracking catalyst having a high yield of light oil and preparation methods thereof. The catalyst comprises 2 to 50% by weight of a magnesium-modified ultra-stable rare earth type Y molecular sieve, 0.5 to 30% by weight of one or more other molecular sieves, 0.5 to 70% by weight of clay, 1.0 to 65% by weight of high-temperature-resistant inorganic oxides, and 0.01 to 12.5% by weight of rare earth oxide. The magnesium-modified ultra-stable rare earth type Y molecular sieve is obtained by the following manner: the raw material, a NaY molecular sieve, is subjected to a rare earth exchange, a dispersing pre-exchange, a magnesium salt exchange modification, an ammonium salt exchange for sodium reduction, a second exchange and a second calcination. The catalyst provided in the present invention is characteristic in its high conversion capacity of heavy oil and a high yield of light oil.

摘要翻译： 本发明涉及一种具有高产率的轻油的重油催化裂化催化剂及其制备方法。 该催化剂包含2至50重量％的镁改性的超稳定稀土Y型分子筛，0.5至30重量％的一种或多种其它分子筛，0.5至70重量％的粘土，1.0至65 的耐高温无机氧化物，0.01〜12.5重量％的稀土类氧化物。 通过如下方式获得镁改性的超稳定稀土类Y分子筛：将原料NaY分子筛进行稀土交换，分散预交换，镁盐交换改性， 铵盐交换用于钠还原，第二次交换和第二次煅烧。 本发明提供的催化剂的特征在于其重油的高转化率和高产率的轻质油。