WO2007006238A1 - Catalyseur de preparation de dimethyle ether par deshydratation de methanol en phase liquide ou mixte - Google Patents

Catalyseur de preparation de dimethyle ether par deshydratation de methanol en phase liquide ou mixte Download PDF

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Publication number
WO2007006238A1
WO2007006238A1 PCT/CN2006/001677 CN2006001677W WO2007006238A1 WO 2007006238 A1 WO2007006238 A1 WO 2007006238A1 CN 2006001677 W CN2006001677 W CN 2006001677W WO 2007006238 A1 WO2007006238 A1 WO 2007006238A1
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Prior art keywords
catalyst
methanol
dimethyl ether
reaction
zsm
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PCT/CN2006/001677
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English (en)
Chinese (zh)
Inventor
Zhongmin Liu
Xinde Sun
Lei Xu
Shuanghe Meng
Shukui Zhu
Zhihui Lv
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Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences
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Application filed by Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences filed Critical Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences
Publication of WO2007006238A1 publication Critical patent/WO2007006238A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
    • 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
    • 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
    • B01J2229/36—Steaming
    • 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
    • B01J29/40—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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta

Definitions

  • the invention relates to a catalyst for liquid phase or mixed phase dehydration of methanol to produce dimethyl ether, in particular to a solid acid catalyst consisting of molecular sieve and binder, which can make methanol in liquid phase or gas-liquid mixed state.
  • a dehydration reaction occurs to form dimethyl ether with high selectivity.
  • Chinese patent CN 1036199A discloses a method for producing dimethyl ether from methanol.
  • the methanol vapor is dehydrated on a ⁇ -alumina catalyst containing a small amount of silica, and the dehydrated product is sent to a rectification column for rectification, pure dimethyl
  • the ether and impurities are separately produced as side product on a certain tray of the column.
  • Chinese patent CN 1125216 discloses a method for producing dimethyl ether from methanol, wherein a content of 72 to 99.9% of methanol is subjected to gas phase catalytic dehydration in a multistage chilled reactor after removing high boilers and impurities through a gasification separation column.
  • a composite solid acid catalyst containing ⁇ -alumina and aluminosilicate crystals is used, the reaction temperature is 190 to 380 Torr, and the methanol conversion is ⁇ 78%.
  • Chinese patent CN 1322704 discloses a method for producing dimethyl ether from methanol, which uses a liquid composite acid composed of sulfuric acid and phosphoric acid as a catalyst to destroy the azeotropy of single sulfuric acid and water, and overcomes the difficulty of moisture when a single sulfuric acid is used as a catalyst.
  • the disadvantage of evaporation and high acidity in the gas phase reduces equipment corrosion.
  • the methanol vapor is subjected to a dehydration reaction by contacting with a liquid complex acid catalyst at a reaction temperature of 130 to 180 ° C and a reaction pressure of 0 to 0.03 MPa, and the reaction mixture is simultaneously vaporized in the reactor to be separated from the catalyst.
  • Chinese Patent Publication No. CN 1073979C discloses a method for producing and recovering dimethyl ether from methanol, that is, when unreacted methanol is separated from water rectification to recycle, the molar ratio of water to methanol in the recycled material is 0.8 to 1
  • the load of the unreacted methanol distillation process can be significantly reduced, and the fresh methanol feedstock can also contain 3 to 10% by weight of water while maintaining a methanol conversion rate of 76% or more.
  • Chinese patent CN 1111231 discloses a method for preparing dimethyl ether by catalytic distillation.
  • the catalytic distillation column is composed of a reaction kettle and a rectification column.
  • the reaction vessel is filled with sulfuric acid having a concentration of 20 to 98% by weight as a catalyst, and the methanol is fed at a position of the fifth theoretical plate number of the rectification column at 100.
  • Dehydration reaction is carried out at a reaction temperature of ⁇ 150 ° C and a reaction pressure of 0.05 to 0.15 MPa absolute, and heavy components such as methyl hydrogen sulfate and dimethyl sulfate are concentrated in the lower portion of the column, and continue in the reaction vessel.
  • Methanol reacts to form a chemical equilibrium, light component dimethyl ether, unreacted nail
  • the alcohol and water are concentrated in the upper portion of the column, thereby inhibiting the formation of by-products and improving the selectivity of dimethyl ether, and the single-pass conversion rate of methanol is 69 to 78%.
  • China Patent Licensing Publication No. CN 1043739C, 1047105C 1085647C and Chinese Patent Publication No. CN 1199038, etc. disclose a catalyst and a process for directly converting synthesis gas into dimethyl ether, and a composite catalyst prepared by mixing an industrial synthetic methanol catalyst with an acidic component catalyst.
  • the reaction temperature is 200 to 400 ° C
  • the reaction pressure is 2 to 5 MPa
  • the carbon monoxide conversion rate is 90%
  • the dimethyl ether selectivity is 90% or more.
  • An object of the present invention is to provide a catalyst for producing dimethyl ether by dehydration reaction of methanol in a liquid phase or a gas-liquid mixture.
  • Still another object of the present invention is to provide an application of the above catalyst for producing dimethyl ether by dehydration reaction in a liquid phase or a gas-liquid mixed state of methanol.
  • the present invention provides the following items:
  • a catalyst for producing dimethyl ether by dehydration reaction of methanol in a liquid phase or a gas-liquid mixture comprising 50 to 95% molecular sieve by weight of dry basis and 5 to 50% by weight of dry basis weight. The composition of the knot.
  • the catalyst provided by the present invention may be a catalyst composed of 50 to 95% (dry basis weight) of molecular sieves and 5 to 50% (dry basis weight) of a binder.
  • the molecular sieve may be a crystalline aluminosilicate or a silicon-containing phosphorous aluminum molecular sieve such as ZSM-5, ZSM-1 K ZSM-22, ZSM-23, Y, mordenite, beta zeolite, MCM-22, MCM- 41.
  • molecular sieves such as ZSM-5, MCM-22, and ⁇ zeolite have high methanol dehydration activity.
  • the molecular sieve-containing catalyst of the present invention may be obtained by a usual hydrothermal synthesis method or other methods, and after being calcined at 500 to 600 ° C for 1 to 30 hours to remove the templating agent, ammonium ion exchange is carried out by a conventional method.
  • the molecular sieve raw powder may be first mixed with a binder, extruded, and then calcined to remove the templating agent, ammonium exchange, and roasting and deamination.
  • the step of calcining the templating agent may also be carried out together with the calcination deamination after the ammonium exchange. Other forming methods other than extrusion can also be taken.
  • the binder is typically alumina, which acts to maintain the shape and strength of the catalyst.
  • the steam-treated catalyst of the molecular sieve-containing catalyst of the present invention can improve the stability of the catalyst and prolong the life of the catalyst.
  • the steam treatment temperature is generally from 250 to 700 ° C, and the preferred temperature range is from 400 to 600 ° C. Steam treatment under appropriate conditions is also beneficial to increase the reactivity of the catalyst.
  • the catalyst of the present invention is suitable for carrying out a methanol dehydration reaction in a liquid phase or a gas-liquid phase mixture.
  • the reaction temperature 120 ⁇ 220 ° C can be used, and the reaction pressure should be such that the reaction mixture is in a liquid phase or a gas-liquid mixed state, generally 0.6 to 8.0 MPa (in the present specification, the gauge pressure), and the methanol feed volume space velocity is 0.1 to 10 ml of methanol / (ml of catalyst, hour).
  • the preferred reaction temperature is from 150 to 200 ° C, the corresponding reaction pressure is from 1.3 to 6.0 MPa, and the methanol feed volume space velocity is from 0.3 to 5 ml of methanol / (ml of catalyst, hour). Regardless of carbon deposition, the selectivity of dimethyl ether can reach 100%.
  • the reaction of dehydration of methanol to dimethyl ether is an exothermic reaction limited by chemical equilibrium, and the lower the temperature, the lower the equilibrium.
  • the higher the conversion rate, the lower the reaction temperature favors the forward movement of the methanol dehydration reaction and increases the methanol conversion rate.
  • the dimethyl ether is enriched in the gas phase, which greatly reduces the concentration of dimethyl ether in the liquid phase reaction mixture on the catalyst surface, thereby breaking the chemical equilibrium limit and increasing the single-pass conversion rate of methanol.
  • the carbon deposit on the surface of the catalyst is mainly derived from hydrocarbon by-products formed from dimethyl ether.
  • dimethyl ether is enriched in the gas phase, which greatly slows down the carbon deposition rate on the surface of the catalyst, and the liquid phase material has a certain dissolution and scouring effect on the carbon deposition precursor on the catalyst surface, so the catalyst of the invention has good performance. Stability and long life.
  • the catalyst of the present invention can be used in a fixed bed reactor or a catalytic distillation reactor.
  • methanol having a content of 50 to 99.9% by weight or more may be used as a raw material.
  • methanol having a content of 5 to 99.9% by weight or more may be used as a raw material.
  • reaction temperature 170 ° C
  • reaction pressure gauge pressure
  • methanol feed space velocity 3.0 ml methanol / (ml catalyst ⁇ hour)
  • the methanol conversion rate was 48.6%
  • the dimethyl ether selectivity was 100%.
  • reaction temperature 155 ° C Under the conditions of reaction temperature 155 ° C, reaction pressure (gauge pressure) 2.1 MPa, methanol feed space velocity 3.0 ml methanol / (ml catalyst, hour), the methanol conversion rate was 6.7%, and the dimethyl ether selectivity was 100%. .
  • reaction temperature 192 ° C
  • reaction pressure gauge pressure
  • methanol feed space velocity 0.92 ml methanol / (ml catalyst ⁇ hour)
  • the methanol conversion rate was 67.5%
  • the dimethyl ether selectivity was 100%.
  • reaction temperature 176 ° C
  • reaction pressure gauge pressure
  • methanol feed space velocity 0.8 ml methanol / (ml catalyst, hour)
  • the methanol conversion rate was 84.9%
  • the dimethyl ether selectivity was 100%.
  • the methanol conversion was 83.7 °/ at a reaction temperature of 200 ° C, a reaction pressure (gauge pressure) of 5.5 MPa, a methanol feed space velocity of 2.0 methanol / (ml of catalyst ⁇ hour).
  • the selectivity to dimethyl ether is 100%.
  • reaction pressure gauge pressure 7.6 MPa
  • methanol feed space velocity 3.5 ml methanol / (ml catalyst ⁇ hour)
  • the methanol conversion rate was 65.2%
  • the dimethyl ether selectivity was 100%.
  • reaction temperature 145 ° C
  • reaction pressure 3.0 MPa
  • methanol feed space velocity 3.5 ml methanol / (ml catalyst ⁇ hour)
  • the methanol conversion rate was 24.1%
  • the dimethyl ether selectivity was 100%.
  • reaction temperature 190 ° C
  • reaction pressure gauge pressure
  • methanol feed space velocity 10 ml methanol / (ml catalyst ⁇ hour)
  • the methanol conversion rate was 35.2%
  • the dimethyl ether selectivity was 100%.
  • reaction temperature 150 ° C Under the conditions of reaction temperature 150 ° C, reaction pressure (gauge pressure) 2.1 MPa, methanol feed space velocity 2.5 ml methanol / (ml catalyst ⁇ hour), the methanol conversion rate was 12.0%, and the dimethyl ether selectivity was 100%. .
  • reaction pressure gauge pressure
  • methanol feed space velocity 4.0 ml methanol / (ml catalyst, hour)
  • the methanol conversion rate was 85.7%
  • the dimethyl ether selectivity was 100%.
  • reaction pressure gauge pressure
  • methanol feed space velocity 2.0 ml methanol / (ml catalyst, hour)
  • the methanol conversion rate was 70.8%
  • the dimethyl ether selectivity was 100%.
  • SAPO-5 zeolite raw powder P:Si:Al atomic ratio of 0.91:0.11:1, dry basis content of 86.6 wt%) and 10.8 g of pseudo-boehmite (produced by Shandong Aluminum Co., Ltd., dry basis content 68.7 % by weight and 0.9 g of tianjing powder are uniformly mixed, 15 ml of 5% by weight of dilute nitric acid is added, and extruded into strips to form a strip shape of 2 mm in diameter, dried at 120 ° C for 2 hours, and calcined at 550 Torr for 4 hours in a muffle furnace. , ⁇ into a strip catalyst of 2 ⁇ 3 mm long.
  • reaction temperature 181 ° C
  • reaction pressure gauge pressure
  • methanol feed space velocity 8.0 ml methanol / (ml catalyst ⁇ hour)
  • the methanol conversion rate was 28.9%
  • the dimethyl ether selectivity was 100 °. /. .
  • SAPO-1 1 zeolite raw powder P:Si:Al atomic ratio of 0.85:0.26: 1, dry basis content of 90.6 wt%) and 38 g of pseudo-boehmite (produced by Shandong Aluminum Co., Ltd., dry basis content) 68.7 wt%) and 3.3 g of tianjing powder were uniformly mixed, 60 ml of 5% by weight of dilute nitric acid was added, and extruded into strips to form a strip of 2 mm in diameter, dried at 120 ° C for 2 hours, and calcined at 550 V in a Mafu furnace. 24 hours, smashed into strips of 2 to 3 mm long catalyst.
  • SAPO-34 zeolite raw powder P:Si:Al atomic ratio of 0.79:0.45:1, dry basis content of 77.2% by weight
  • pseudo-boehmite produced by Shandong Aluminum Co., Ltd., dry content 68.7
  • % by weight and 1.2 g of tianjing powder were uniformly mixed, and 24 ml of 5% by weight of dilute nitric acid was added, and extruded into strips to prepare a strip shape of 2 mm in diameter, dried at 120 Torr for 2 hours, and calcined at 550 ° C for 4 hours in a muffle furnace. , ⁇ into a strip catalyst of 2 ⁇ 3 mm long.
  • reaction pressure gauge pressure
  • methanol feed space velocity 3.0 ml methanol / (ml catalyst ⁇ hour)
  • the methanol conversion rate was 56.8%
  • the dimethyl ether selectivity was 100%.
  • the NH 4 N0 3 aqueous solution was exchanged 3 times at 85 ° C, washed 3 times with deionized water, dried at 120 ° C for 2 hours, calcined at 550 ° C for 3 hours, and kneaded into a strip catalyst of 2 to 3 mm length.
  • reaction pressure gauge pressure
  • methanol feed space velocity 4.0 ml methanol / (ml catalyst, hour)
  • the methanol conversion rate was 69.1%
  • the dimethyl ether selectivity was 100%.
  • the NH 4 N0 3 aqueous solution of M was exchanged 3 times at 85 ° C, washed 3 times with deionized water, dried at 120 ° C for 2 hours, calcined at 550 ° C for 3 hours, and kneaded into a strip catalyst of 2 to 3 mm length.
  • reaction pressure gauge pressure
  • methanol feed space velocity 8.0 ml methanol / (ml catalyst ⁇ hour)
  • the methanol conversion rate was 29.6%
  • the dimethyl ether selectivity was 100%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural 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

Ce catalyseur de préparation de diméthyle éther par déshydratation de méthanol en phase liquide ou mixte, comprenant un liquide et un gaz, comporte entre 50 et 95 % de tamis moléculaire (poids de base sec) et entre 5 et 50 % de liant (poids de base sec). Le tamis moléculaire est sélectionné dans le groupe constitué ZSM-5, ZSM-11, ZSM-22, ZSM-23, Y, mordénite, ß zéolite, MCM-22, MCM-41, MCM-56, MCM-49, SAPO-5, SAPO-11, SAPO-34. Ce tamis moléculaire est de préférence ZSM-5, ß ou MCM-22.Le catalyseur fait preuve d'une forte activité de déshydratation de méthanol et d'une forte sélectivité de diméthyle éther atteignant jusqu'à 100 % dans un réacteur à lit fixe dans des conditions réactionnelles où la température de réaction est comprise entre 100 et 220, la pression de réaction est comprise entre 0,6 et 8.0 MPa, la vitesse spatiale d'alimentation est de 0,1 à 10ml méthanol/(ml catalyst.hr).La stabilité du catalyseur peut être augmentée par traitement à la vapeur.
PCT/CN2006/001677 2005-07-14 2006-07-14 Catalyseur de preparation de dimethyle ether par deshydratation de methanol en phase liquide ou mixte WO2007006238A1 (fr)

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Application Number Priority Date Filing Date Title
CN200510012180.6 2005-07-14
CN 200510012180 CN1895776B (zh) 2005-07-14 2005-07-14 一种用于甲醇液相或混相脱水生产二甲醚的催化剂

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100076227A1 (en) * 2007-03-30 2010-03-25 China Petroleum & Chemical Corporation Fluidized catalytic process for production of dimethyl ether from methanol
CN113677654A (zh) * 2019-02-22 2021-11-19 英国石油有限公司 方法
EP3927680A4 (fr) * 2019-02-22 2022-11-02 Bp P.L.C. Procédé
CN115283009A (zh) * 2022-08-11 2022-11-04 扬州晨化新材料股份有限公司 一种用于连续合成聚氨酯用叔胺类催化剂的含sapo-34分子筛组合物及其制备方法

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CN101279282B (zh) * 2007-04-04 2011-04-27 中国石油化工股份有限公司 用于甲醇制丙烯的zsm-5介孔分子筛催化剂及其制备方法
CN102060644B (zh) * 2009-11-17 2013-07-10 中国石油化工集团公司 一种甲醇脱水制烯烃方法
CN102060645B (zh) * 2009-11-17 2013-07-24 中国石油化工集团公司 一种甲醇脱水制烯烃工艺
CN102671690B (zh) * 2011-12-14 2015-04-22 河南科技大学 一种甲醇制二甲醚用催化剂及其制备方法
CN106032280B (zh) * 2015-03-17 2018-11-30 中国科学院大连化学物理研究所 一种具有介孔和微孔的丝光沸石的合成方法、产品及其应用
CN104841479B (zh) * 2015-04-15 2017-09-08 西安近代化学研究所 一种复合固体酸胺化催化剂及其制备方法
CN106466626A (zh) * 2015-08-20 2017-03-01 中国石油化工股份有限公司 无粘结剂zsm-22/sapo-34复合分子筛及其制备方法和用途
CN106466630A (zh) * 2015-08-20 2017-03-01 中国石油化工股份有限公司 无粘结剂zsm-23/sapo-34复合分子筛及其制备方法
CN105107544A (zh) * 2015-08-24 2015-12-02 北京理工大学 一种二甲醚生产用固体酸催化剂及其制备方法
CN105688881B (zh) * 2016-02-25 2018-07-31 洛阳市科创石化科技开发有限公司 一种合成烷撑二醇醚的催化剂及其制备方法和应用

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100076227A1 (en) * 2007-03-30 2010-03-25 China Petroleum & Chemical Corporation Fluidized catalytic process for production of dimethyl ether from methanol
US8304582B2 (en) * 2007-03-30 2012-11-06 China Petroleum & Chemical Corporation Fluidized catalytic process for production of dimethyl ether from methanol
CN113677654A (zh) * 2019-02-22 2021-11-19 英国石油有限公司 方法
EP3927681A4 (fr) * 2019-02-22 2022-11-02 Bp P.L.C. Procédé
EP3927680A4 (fr) * 2019-02-22 2022-11-02 Bp P.L.C. Procédé
CN113677654B (zh) * 2019-02-22 2023-10-10 英国石油有限公司 方法
US12084410B2 (en) 2019-02-22 2024-09-10 BP P.L.C. and BP (CHINA) Holdings LTD Process for dehydrating methanol to dimethyl ether
US12084409B2 (en) 2019-02-22 2024-09-10 Bp P.L.C. Process for dehydrating methanol to dimethyl ether
CN115283009A (zh) * 2022-08-11 2022-11-04 扬州晨化新材料股份有限公司 一种用于连续合成聚氨酯用叔胺类催化剂的含sapo-34分子筛组合物及其制备方法

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CN1895776B (zh) 2012-07-25

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