Petrochina Company Limited

Hongchang Duan

Haitao Zhang

Di Li

Xionghou Gao

Zhengguo Tan

Chenxi Zhang

Yunfeng Zheng

Xiaoliang Huang

Jinjun Cai

Xueli Li

Dong Ji

Gengzhen Cao

Zhishuang Pan

Chaowei Liu

ZhengGuo Tan

Yi Su

Yi Wang

Yanqing Ma

Yanbo Sun

Dong Wang

Lin Wang

Shuhong Sun

Yahong Wang

Xueqin Sun

Zhicheng Tang

Chengyuan Yuan

The invention relates to a molecular sieve modification method and a catalytic cracking catalyst containing a molecular sieve. The method comprises: mixing a solution containing an ion of a Group MB metal in the periodic table, an organic complexing agent, and/or a dispersant and a precipitation agent, and stirring the same to form a suspension containing a precipitant of a Group IIIB element; and mixing the resulting precipitant and a molecular sieve slurry, stirring the same to obtain a mixed slurry containing the precipitant of the Group MB element and a molecular sieve, and performing spray drying and optional calcination, to obtain a modified molecular sieve. The catalyst comprises, as calculated based on the catalyst mass being 100%, 10-55% of a modified molecular sieve (on a dry basis), 10-80% of clay (on a dry basis), 0-40% of an inorganic oxide (on an oxide basis), and 5-40% of a binding agent (on an oxide basis). The catalyst has good activity stability and heavy metal contamination resistance.

Method for modifying molecular sieve and a catalytic cracking catalyst containing the molecular sieve

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 &#x201c;second exchange and second calcination&#x201d; 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.

Catalytic cracking catalyst for high-efficiency conversion of heavy oil and preparation method thereof

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.

Phosphorus-containing ultrastable Y-type rare earth molecular sieve and preparation method therefor

A method for producing double-component modified molecular sieve comprises adding molecular sieve to an aqueous solution containing phosphorus to form a mixture, allowing the mixture to react at pH of 1-10, temperature of 70-200&#xb0; C. and pressure of 0.2-1.2 MPa for 10-200 min, and then filtering, drying and baking the resultant to obtain phosphorus-modified molecular sieve, and then adding the phosphorus-modified molecular sieve to an aqueous solution containing silver ions, allowing the phosphorus-modified molecular sieve to react with silver ions at 0-100&#xb0; C. in dark condition for 30-150 min, and then filtering, drying and baking. The obtained double-component modified molecular sieve contains 88-99 wt % molecular sieve with a ratio of silica to alumina between 15 and 60, 0.5-10 wt % phosphorus (based on oxides) and 0.01-2 wt % silver (based on oxides), all based on dry matter. A catalyst produced from the double-component modified molecular sieve has improved hydrothermal stability and microactivity.

Double-component modified molecular sieve with improved hydrothermal stability and production method thereof

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.

High light received heavy oil catalytic cracking catalyst and preparation method therefor

The present invention relates to a heavy oil catalytic cracking catalyst and preparation method thereof. The catalyst comprises 2 to 50% by weight of an 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 ultra-stable rare earth type Y molecular sieve is obtained as follows: the raw material, NaY molecular sieve, is subjected to a rare earth exchange and a dispersing pre-exchange, and the molecular sieve slurry is filtered, washed and subjected to a first calcination to produce a 'one-exchange one-calcination' rare earth sodium Y molecular sieve, wherein the order of the rare earth exchange and the dispersing pre-exchange is not limited; and the 'one-exchange one-calcination' rare earth sodium Y molecular sieve is further subjected to ammonium salt exchange for sodium reduction and a second calcination. The catalyst provided in the present invention is characteristic in its high heavy-oil-conversion capacity, a high total liquid yield and a high light oil yield.

Heavy oil catalytic cracking catalyst and preparation method therefor

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 &#x3bc;m and a D(v,0.9) of not more than 20 &#x3bc;m. 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.

Magnesium modified ultra-stable rare earth Y-type molecular sieve and preparation method therefor

The present invention provides an 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. The molecular sieve comprises 1 to 20% by weight of rare earth oxide, not more than 1.2% by weight of sodium oxide, has a crystallinity of 51 to 69%, and a lattice parameter of 2.451 nm to 2.469 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 &#x3bc;m and a D(v,0.9) of not more than 20 &#x3bc;m. 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.

Ultra-stable rare earth Y-type molecular sieve and preparation method therefor

Modified molecular sieve characterized by improved sodium-resisting contamination activity and preparation method thereof are provided. The method comprises: adding molecular sieve in phosphorus-containing organic solution, and reacting for 10-200 minutes at temperature of 70-200&#xb0; C. and pressure of 0.2-1.2 MPa, and then filtering, drying and calcining. The said modified molecular sieve contains 90-99 wt. % molecular sieve as dry basis and 1-10 wt. % phosphorus as oxide. The said method can improve the capability of sodium-resisting contamination effectively, and its technology is simple and fits the existing catalyst production apparatus and process. The said modified molecular sieve has high sodium-resisting contamination activity, and the model catalyst by sodium contamination has high activity retention.

Modified molecular sieve characterized by improved sodium-contamination-resisting activity and preparation method thereof

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Beijing, China

Hongchang Duan