CN1292831C - High-performance variable-pressure adsorption 5A molecular sieve and preparing method thereof - Google Patents
High-performance variable-pressure adsorption 5A molecular sieve and preparing method thereof Download PDFInfo
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- CN1292831C CN1292831C CNB031157432A CN03115743A CN1292831C CN 1292831 C CN1292831 C CN 1292831C CN B031157432 A CNB031157432 A CN B031157432A CN 03115743 A CN03115743 A CN 03115743A CN 1292831 C CN1292831 C CN 1292831C
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Abstract
The present invention relates to a preparation method for high performance pressure swing adsorption 5A molecular sieves. The present invention comprises the processing steps that 1, 80 to 90 wt% of 4A molecular sieve initial powder is mixed with 5 to 20 wt% of kaolin clay, and 1 to 50 wt% of additive vegetable fiber is added in a high-speed granulator for granulation; 2, granular intermediate products after the granulation can be sieved according to product fineness requirements and are calcined at high temperature of 200 to 1000 DEG C after being dried; 3, the intermediate products after being calcined are soaked in 4 to 25 wt% of sodium hydroxide solution for alkali inlet treatment, 2 to 20 wt% of CaCl2 solution is used for Ca<2+> exchange after washing, granular products are calcined for a second time at 100 to 800 DEG C after being washed and dried, and then the high performance pressure swing adsorption 5A molecular sieve can be obtained. The 5A molecular sieve of the present invention has the advantages of large absorption capacity, high diffusion rate and high mechanical strength and is used for pressure swing adsorption oxygen preparation, hydrogen preparation, petroleum dewaxing, etc.
Description
Technical field
The present invention relates to a kind of transformation absorption (being called for short PSA) system oxygen that is used for, high-performance transformation absorption 5A molecular sieve of hydrogen manufacturing and oil dewaxing and preparation method thereof.
Background technology
The characteristics of transformation absorption (PSA) process are to carry out the absorption and the desorb of molecular sieve by changing pressure and temperature, and adsorption cycle is short, switches frequently, and pressure changes greatly.Therefore the diffusion rate to molecular sieve requires height, and is also higher to the requirement of mechanical strength of molecular sieve.
The preparation method of traditional PSA zeolite product is through Ca with the 4A molecular screen primary powder
2+After the exchange, add the adhesive roller forming, make after the roasting again.Molecular sieve through roasting, is bonded together adhesive and molecular screen primary powder, and has certain intensity after moulding.And also formed so-called secondary pore (being different from the micropore of molecular sieve crystal inside) between the molecular screen primary powder particles.The secondary pore structure of molecular sieve has a significant impact the mechanical strength and the diffusion rate of product.Often when having preferably mechanical strength, its adsorbance is just lower with the molecular sieve of conventional method preparation, and diffusion rate is also slow; And if reduce the binder use amount, can improve adsorbance to a certain extent, but mechanical strength can reduce again, can not satisfy the requirement of use.
U.S. Pat P3,394,989 method is to add a small amount of 4A molecular screen primary powder with clay, preformed is after alkali treatment, to improve the pore structure of product.Disclose a kind of preparation method of 5A molecular sieve among the Chinese patent CN92111878.3, it is to adopt 4A molecular sieve powder to add the clay of 15-35% and the plant amylum moulding of 0.2-2%, again through alkali treatment and Ca
2+The 5A molecular sieve is made in exchange.Because the addition of clay is bigger, so its adsorbance and diffusion rate are lower.
Summary of the invention
The purpose of this invention is to provide a kind of high-performance transformation absorption 5A molecular sieve with higher rate of diffusion and higher mechanical strength.
The preparation method of transformation absorption 5A molecular sieve of the present invention comprises following processing step:
(1) the 4A molecular screen primary powder of 80-95 weight portion mixes with the adhesive of 5-20 weight portion, adds the additive plant fiber powder of 1-50 weight portion, and at high speed granulator high speed stirring-granulating, the rotating speed of high speed granulator is 200-1000 rev/min.
(2) the graininess intermediate product after the granulation is sieved according to the fineness of product requirement, oven dry is after 200 ℃ of-1000 ℃ of high-temperature roastings.
(3) carry out alkali treatment in the sodium hydroxide solution of the immersion of the intermediate product after roasting 4-25% percentage by weight, the washing back CaCl of 2-20% percentage by weight
2Solution carries out Ca
2+Exchange after washing, the oven dry, is carried out after baking with this granular disintegration at 100 ℃-800 ℃, obtains high-performance transformation absorption 5A zeolite product.
Adhesive among the present invention is the kaolin families clay, and addition is that the 6-12 weight portion is better.
The fineness of the plant fiber powder among the present invention is 100 orders-1000 orders, and addition is that the 2-10 weight portion is better.
Plant fiber powder among the present invention is by choosing any one kind of them in plant shell, axis, the plant bar or two or morely making through pulverizing.
In the processing step of the present invention (3), the intermediate product after the roasting washs the CaCl of back with the 2-20% percentage by weight with the sodium hydroxide solution impregnation process of 4-25% percentage by weight
2Solution carries out Ca
2+Exchange.The liquid material weight ratio of wherein said sodium hydroxide solution and intermediate product is 3-14: 1, and described CaCl
2Contained pure CaCl in the solution
2With the weight of intermediate product be 0.4-0.8: 1.
The particle diameter of the transformation absorption 5A zeolite product that makes among the present invention is 0.4-2.5mm.
In preparation process of the present invention, reduce the addition of binding agent, can improve the adsorption capacity of product, add plant fiber powder, can improve the loose structure of product, improve the diffusion rate of product.With the granulation of high speed granulator, keep high-speed stirred, thereby obtain having the intermediate products of higher-strength, the particle diameter of intermediate products is better between 0.4-2.5mm; Intermediate products need through 200 ℃ of-1000 ℃ of high-temperature roastings, to guarantee carrying out smoothly with post processing; Product after the roasting is handled with NaOH solution, uses CaCL after the washing
2Solution exchanges, washs, obtain product through 100 ℃ of-800 ℃ of roastings again after the drying.
Compared with prior art, the present invention has following characteristics: one, owing to reduced adhesive consumption in the preparation of molecular sieve, improved the adsorption capacity of product.Two, add plant fiber powder, improved the loose structure of product, improved the diffusion rate of product.Three, improved the mechanical strength of product by the high speed granulation.
The specific embodiment
Now in conjunction with the embodiments, content of the present invention is further described.
Embodiment 1
94 parts of (weight) 4A molecular screen primary powders mix with 6 parts of (weight) kaolin; add plant fiber powder (plant shell system; cross 320 orders) 1.5 parts (weight) stir granulation in 10 minutes in high speed granulator high speed; through sieve the intermediate product of φ 1.6-2.5mm; oven dry is after 800 ℃ of roastings; the CaCl of back with 4% (weight) washed in alkali treatment in the sodium hydroxide solution of the intermediate product immersion 5% (weight) after the roasting
2Solution carries out Ca
2+The exchange, after the washing and drying 500 ℃ of following roastings.The product strength that obtains is 33 newton; Measure its H with the BET method
2The O adsorbance is 26.02% during relative humidity 50%; With its diffusion rate of chromatography determination O
2Be 1.04 * 10
-2Cm
2/ second, N
2Be 1.03 * 10
-3Cm
2/ second; Measure its oxygen enrichment ability O with dynamics evaluation apparatus
2Be 92.6% o'clock, pure O
2Productive rate be 20.05 standard liters/hour. the kilogram.
Embodiment 2
After 92 parts of (weight) 4A molecular screen primary powders and 8 parts of (weight) kaolin mix; add plant fiber powder (plant shell system; cross 320 orders) 1.5 parts (weight); stir granulation in 10 minutes in high speed granulator high speed; through sieve the intermediate product of φ 1.6-2.5mm; oven dry is after 800 ℃ of roastings, and the intermediate product after the roasting immerses alkali treatment in the sodium hydroxide solution of 10% (weight), and the washing back is with the CaCl of 6% (weight)
2Solution carries out Ca
2+Exchange, 500 ℃ of roastings, the product strength that obtains is 33 newton after the washing and drying; Measure its H with the BET method
2The O adsorbance is 26.07% during relative humidity 50%; With its diffusion rate of chromatography determination O
2Be 1.05 * 10
-2Cm
2/ second, N
2Be 1.04 * 10
-3Cm
2/ second, measure its oxygen enrichment ability O with dynamics evaluation apparatus
2Be 92.7% o'clock, pure O
2Productive rate be 20.00 standard liters/hour. the kilogram.
Embodiment 3
90 parts of (weight) 4A molecular screen primary powders mix with 10 parts of (weight) kaolin; add plant fiber powder (axis system; cross 400 orders) 5 parts (weight); stirred 10 minutes in high speed granulator high speed; obtain the intermediate product of φ 0.4-0.85mm through screening; oven dry is after 700 ℃ of roastings, and the intermediate product after the roasting immerses alkali treatment in the sodium hydroxide solution of 15% (weight), and the washing back is with the CaCl of 10% (weight)
2Solution carries out Ca
2+Exchange, washing, oven dry back are 400 ℃ of following roastings, and the product strength that obtains is 35 newton, surveys its H with the BET method
2The O adsorbance is 27.16% during relative humidity 50%; With its diffusion rate of chromatography determination O
2Be 1.14 * 10
-2Cm
2/ second, N
2Be 3.20 * 10
-3Cm
2/ second, measure its oxygen enrichment ability O with dynamics evaluation apparatus
2Be 92.5% o'clock, pure O
2Productive rate be 23.10 standard liters/hour. the kilogram.
Embodiment 4
88 parts of (weight) 4A molecular screen primary powders mix with 12 parts of (weight) kaolin; add the fine thing powder of plant (plant bar system; cross 250 orders) 30 parts (weight); stirred 20 minutes in high speed granulator high speed; obtain the intermediate product of φ 1.6-2.5mm through screening; oven dry is after 800 ℃ of roastings, and the intermediate product after the roasting immerses alkali treatment in the sodium hydroxide solution of 20% (weight), and the washing back is with the CaCl of 15% (weight)
2Solution carries out Ca
2+Exchange, washing, oven dry back are 500 ℃ of following roastings, and the product strength that obtains is 41 newton, surveys its H with the BET method
2The O adsorbance is 25.29% during relative humidity 50%; With its diffusion rate of chromatography determination O
2Be 4.38 * 10
-3Cm
2/ second, N
2Be 1.04 * 10
-3Cm
2/ second, measure its oxygen enrichment ability O with dynamics evaluation apparatus
2Be 93.1% o'clock, pure O
2Productive rate be 20.89 standard liters/hour. the kilogram.
Embodiment 5
82 parts of (weight) 4A molecular screen primary powders mix with 20 parts of (weight) kaolin; add plant fiber powder (axis system; cross 250 orders) 50 parts (weight); stirred 20 minutes in high speed granulator high speed; obtain the intermediate product of φ 1.6-2.5mm through screening; oven dry is after 800 ℃ of roastings, and the intermediate product after the roasting immerses alkali treatment in the sodium hydroxide solution of 25% (weight), and the washing back is with the CaCl of 10% (weight)
2Solution carries out Ca
2+Exchange, washing, oven dry back are 600 ℃ of following roastings, and the product strength that obtains is 40 newton, surveys its H with the BET method
2The O adsorbance is 26.05% during relative humidity 50%; With its diffusion rate of chromatography determination O
2Be 4.40 * 10
-3Cm
2/ second, N
2Be 1.04 * 10
-3Cm
2/ second, measure its oxygen enrichment ability O with dynamics evaluation apparatus
2Be 92.5% o'clock, pure O
2Productive rate is 20.05 standard liters/hour kilogram.
The comparative example
82 parts of (weight) 4A molecular screen primary powders mix the middle product that the back roller forming obtains φ 1.6-2.5mm with 18 parts of (weight) kaolin, oven dry is after 700 ℃ of roastings, the CaCl of back with 10% (weight) washed in alkali treatment in the sodium hydroxide solution of the intermediate product immersion 15% (weight) after the roasting
2Solution carries out Ca
2+Exchange, washing, oven dry back are 500 ℃ of following roastings, and the product strength that obtains is 20 newton, surveys its H with the BET method
2The O adsorbance, relative humidity 50% is 22.85%; With its diffusion rate of chromatography determination O
2Be 6.26 * 10
-4Cm
2/ second, N
2Be 2.35 * 10
-4Cm
2/ second, measure its oxygen enrichment ability O with dynamics evaluation apparatus
2Be 90.0% o'clock, pure O
2Productive rate be 15.4 standard liters/hour. the kilogram.
Claims (6)
1, a kind of preparation method of high-performance transformation absorption 5A molecular sieve is characterized in that comprising following processing step:
(1) the 4A molecular screen primary powder of 80-95 weight portion mixes with the adhesive of 5-20 weight portion, adds the additive plant fiber powder of 1-50 weight portion, and at high speed granulator high speed stirring-granulating, the rotating speed of high speed granulator is 200-1000 rev/min;
(2) the graininess intermediate product after the granulation is sieved according to the fineness of product requirement, oven dry is after 200 ℃ of-1000 ℃ of high-temperature roastings;
(3) carry out alkali treatment in the sodium hydroxide solution of the immersion of the intermediate product after roasting 4-25% percentage by weight, after the washing, with the CaCl of 2-20% percentage by weight
2Solution carries out Ca
2+Exchange after washing, the oven dry, is carried out after baking with this granular disintegration at 100 ℃-800 ℃, gets high-performance transformation absorption 5A zeolite product.
2, the preparation method of 5A molecular sieve according to claim 1 is characterized in that: described adhesive is the kaolin families clay, and addition is the 6-12 weight portion.
3, the preparation method of 5A molecular sieve according to claim 1 and 2 is characterized in that: the fineness of described plant fiber powder is 100 orders-1000 orders, and addition is the 2-10 weight portion.
4, the preparation method of 5A molecular sieve according to claim 1 and 2 is characterized in that: described plant fiber powder is by choosing any one kind of them in plant shell, axis, the plant bar or two or morely making through pulverizing.
5, the preparation method of 5A molecular sieve according to claim 1 is characterized in that the liquid material weight ratio of sodium hydroxide solution described in the step (3) and intermediate product is 3-14: 1, and described CaCl
2Contained pure CaCl in the solution
2With the weight ratio of intermediate product be 0.4-0.8: 1.
6, the preparation method of 5A molecular sieve according to claim 1 is characterized in that the particle diameter of the 5A zeolite product that makes is 0.4-2.5mm.
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| CN1292831C true CN1292831C (en) | 2007-01-03 |
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Families Citing this family (10)
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| CN1329114C (en) * | 2004-12-24 | 2007-08-01 | 上海化工研究院 | Formulation of dry filter core for refrigerating system |
| CN100431689C (en) * | 2006-12-21 | 2008-11-12 | 北京工业大学 | Preparation method of compound absorbent for removing nitrogen oxide |
| CN103028374B (en) * | 2012-12-28 | 2014-12-17 | 天津众智科技有限公司 | 5A molecular sieve with high adsorption rate |
| CN105749859B (en) * | 2014-12-17 | 2018-05-04 | 中国石油天然气股份有限公司 | Preparation method for methyl methacrylate deacidification adsorbent |
| CN106475048B (en) * | 2015-08-28 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of the 5A molecular sieve spherical adsorbent and preparation method of binder free |
| CN107961759B (en) * | 2016-10-19 | 2020-08-11 | 中国石油化工股份有限公司 | 5A molecular sieve adsorbent and preparation method and application thereof |
| CN107376835B (en) * | 2017-08-18 | 2020-12-01 | 洛阳建龙微纳新材料股份有限公司 | Efficient hydrogen production adsorbent and preparation method thereof |
| CN114682237B (en) * | 2020-12-31 | 2023-09-01 | 中国石油化工股份有限公司 | Preparation method of 5A molecular sieve adsorbent |
| CN115672264B (en) * | 2021-07-30 | 2024-02-02 | 中国石油化工股份有限公司 | Preparation method of pressure swing adsorbent |
| CN115155519A (en) * | 2022-08-01 | 2022-10-11 | 中科洁力（福州）环保技术有限公司 | Preparation method of molecular sieve with strong adsorbability |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042021C (en) * | 1992-11-17 | 1999-02-10 | 中国科学院大连化学物理研究所 | Process for preparing adsorbent of non-adhesive dewaxed 5A molecular sieve |
| CN1248487A (en) * | 1998-09-24 | 2000-03-29 | 广州经济技术开发区商业服务总公司 | Secondary perforated molecular siever adsorbent and preparation process thereof |
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- 2003-03-11 CN CNB031157432A patent/CN1292831C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042021C (en) * | 1992-11-17 | 1999-02-10 | 中国科学院大连化学物理研究所 | Process for preparing adsorbent of non-adhesive dewaxed 5A molecular sieve |
| CN1248487A (en) * | 1998-09-24 | 2000-03-29 | 广州经济技术开发区商业服务总公司 | Secondary perforated molecular siever adsorbent and preparation process thereof |
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Owner name: JIANGSHU ALSIO TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: SINOAMERICAN JOINT VENTURE JINZHONG MOLECULAR SIEVES CO., LTD., SHANGHAI Effective date: 20130318 |
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Effective date of registration: 20130318 Address after: 1089 No. 222300 Jiangsu city of Lianyungang province Donghai County jindow Avenue Patentee after: Jiangsu ALSIO Technology Co., Ltd. Address before: 201203 Zhangjiang Road, Zhangjiang Industrial Park, Shanghai, Pudong New Area Patentee before: Sinoamerican Joint Venture Jinzhong Molecular Sieves Co., Ltd., Shanghai |
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