CN1415414A - Catalyzer utilized to synthesize oxalate and its preparation method - Google Patents
Catalyzer utilized to synthesize oxalate and its preparation method Download PDFInfo
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Abstract
A catalyst for synthesizing oxalate is prepared by using delta-Al2O3 as carrier to carry the active components Pd, Fe and La. The said carrier is prepared from alpha-AlO(OH) or Al salt.
Description
Technical Field
The invention relates to synthesis of oxalate, in particular to a catalyst for synthesizing oxalate and a preparation method thereof. The present invention relates to a catalyst for catalytic synthesis of oxalate from carbon monoxide and nitrous acid ester and its preparation method, and provides a delta-Al catalyst suitable for said reaction and prepared by using different methods2O3The crystal form is a carrier, and two or more active components of metal are loaded on the carrier, so that the activity and the service life of the catalyst can be effectively improved by mutual matching.
Background
Oxalate ester can be used for preparing oxalic acid, oxamide, glycol and intermediates of certain drugs and dyes, is an important basic chemical raw material and has important function in carbon-one chemistry, and the discovery of D.M.Fenton et Al in 1965 that carbon monoxide is subjected to coupling reaction in alcohol medium to obtain α -Al2O3The carrier is palladium metal as catalyst to synthesize oxalic diester. Then, considerable expenses are invested in the united states and japan, and research and development are carried out along this concept.
The preparation process of the catalyst uses different active metal components to carry out different proportions, the composition of reaction materials, the reaction temperature, the flow rate of carrier gas, the improvement of equipment and the like, and the used carriers are α -Al2O3Or gamma-Al2O3The crystal form is carrier ((1) Chenoheshen Cichlon Xue Biao Nature gas chemical 1995 Vol 20(2)5-9, He Fei Gangzhenghong Songyu Hua Genghui catalytic Xuanhui Ching 2002523 Vol (3) 223-. Chinese patent CN 1066070C describes the use of activated alumina, but with Al as given2O3Surface area of 6-7M2Per g, should be α -Al2O3EP 0108359A 1 also uses α -Al2O3And (4) preparing a carrier.
We found in our experiments to use α -Al2O3Or gamma-Al2O3The catalyst prepared by using the crystal form as a carrier has lower yield or poorer service life due to the pore structure and strength of the carrier. As shown in table one and table two: table one: catalyst prepared from carriers with different crystal forms, yield and service life comparison
1g.※: the same applies to 1g of catalyst. Table two: structural indexes of carriers of different crystal forms (figure 2: mercury intrusion diagram)
Carrier crystal form | Yield of | Life span |
γ-Al2O3 | 1.22g/lg.※1h | Difference (D) |
δ-Al2O3 | 3.29g/1g1h | Good taste |
δ-Al2O3+α-Al2O3 | 2.33g/1g1h | Is preferably used |
Structural item | γ-Al2O3 | δ-Al2O3 | δ-Al2O3+α-Al2O3 |
Cumulative pore volume (ml/g) | 0.3931 | 0.5578 | 0.5110 |
Total pore specific surface area (sq-m/g) | 166.530 | 68.876 | 62.117 |
Diameter of middle hole (um) | 0.0089 | 0.0376 | 0.0439 |
Apparent Density (g/ml) | 1.3918 | 1,1515 | 1.2483 |
Skeleton density (g/ml) | 3.0736 | 3.2196 | 3.4480 |
Disclosure of Invention
The invention aims to provide a catalyst for synthesizing oxalate and a preparation method thereof, which can overcome the defects of the prior art and adopts delta-Al2O3The crystal form is used as a carrier, has the most appropriate pore structure and strength, and the obtained catalyst has better activity and service life under the same conditions
The invention uses delta-Al2O3The crystal form is used as a carrier to load a catalyst consisting of Pd, Fe and La active components. The atomic ratio of the active ingredients is 3-0.5: 2-0.5 respectively. The delta-Al2O3The pore structure of the carrier is: total pore volume (ml/g) 0.4-0.9; total pore surface area (m)2Per g)60 to 100; average pore diameter (mum) of 0.03-0.05; apparent density (g/ml) 0.77-1.2; the skeleton density (g/ml) is 2.5-3.5.
Delta-Al of the invention2O3The preparation method of the carrier comprises the following steps:
1) preparation of delta-Al from pseudo-boehmite2O3Carrier
Crushing pseudo-boehmite by 200-400#Sieving with a sieve, adding graphite powder 1-3% of the powder and CaCO 1-3% of the powder3Then adding dilute HNO accounting for 45 percent of the powder amount3(concentration is 1-3%), stirring uniformly, and rolling. Extruding into 2.5mm strip with a strip extruder, and naturally drying4 hours, drying at 120 ℃, and roasting according to a certain temperature rising program.
(2) From AlCl3·6H2Preparation of delta-Al from O2O3And (3) a carrier.
5 parts of AlCl with the concentration of 8.6 percent (weight percentage)3·6H2O solution with 1 part of 1% NH4The OH solution is added into the reactor under stirring, and the reaction is carried out at 70 ℃ and the pH value is 7-8. Standing for 30 minutes, filtering, washing with water until no Cl is detected-Until now. Drying at 120 deg.C, adding graphite and CaCO in sequence according to the proportion of (1)3Dilute HNO3Rolling, extruding into cylindrical strips with diameter of 2.5mm, naturally drying for 5 hr, drying at 120 deg.C, and calcining according to a certain program.
Usable Al2(SO4)3·6H2O、Al(NO3)3·6H2O instead of AlCl3·6H2Preparation of delta-Al from O2O3A carrier in a crystal form.
The roasting temperature-rising program is as follows:
keeping the temperature at 200 ℃ for 20-40 min, keeping the temperature at 250 ℃ for 20-35 min, keeping the temperature at 300 ℃ for 2-4 h
Keeping the temperature at 500 ℃ for 20-40 min, keeping the temperature at 600 ℃ for 20-30 min, and keeping the temperature at 900 ℃ for 4-9 hours
Naturally cooling to room temperature. X-ray diffraction pattern 1 shows that 45.4 DEG is delta-Al2O3Minor main peak of (2).
The invention uses delta-Al2O3The preparation method of the catalyst used as the carrier comprises the following steps:
1) the halide, nitrate and sulfate of Pd, Fe and La are used to prepare impregnating solution according to the measurement, and acid is added to control the PH value between 1 and 4.5, so as to prevent the influence of hydroxide precipitation generated by metal ion hydrolysis on the impregnation of the carrier.
2) Providing delta-Al with appropriate pore structure and strength2O3The carrier is added into the impregnation liquid and soaked for 2-8 hours.
3) Separating, drying, soaking in mixed alkali solution at 70 deg.C for 4-6 hr, and washing to remove negative ions.
4)Drying, and treating with H at 550 ℃ under 220-2Reducing for 3-5 hours to prepare different types of catalysts.
The invention uses delta-Al2O3The catalyst used as a carrier is applied to the reaction of synthesizing oxalate by gas phase catalysis of carbon monoxide and nitrite as follows:
coupling reaction: wherein: r alkyl (CH)3-,C2H5-,C4H9-)
And (3) regeneration reaction:
the oxalate synthesis adopts a fixed bed device, the reaction tube is in a jacket structure, the innermost layer of the reaction tube is provided with a hard glass tube with the inner diameter of 10-20mm and the length of 300-350mm, 1-80ml of catalyst can be filled, and the top of the catalyst layer is additionally provided with glass fiber with the thickness of 100mm so as to preheat the reaction feed gas. The middle layer is filled with a heating white oil and mercury conductive meter (used for controlling temperature), the outer wall is wrapped with a layer of asbestos paper, a resistance wire is wound, the outermost layer is protected by asbestos cloth, and the temperature of a catalyst bed layer is controlled by a relay. The reaction tube has three outlets, the middle port in the top is inserted into ground thermometer to measure the temperature in the reaction area, the side port is connected to gasifying tube, the reaction material gas is mixed into the reactor, and the bottom has outflow product and tail gas port. Detecting with 102G gas chromatograph from Shanghai analytical instrument factory, and using 5A molecular sieve as chromatographic column filler with column length of 4 m.
The ratio of CO to RONO is generally controlled to be 15-30 to 10-15 (volume ratio), the contact time is 0.5-3 seconds, the activation temperature of the catalyst is 120-140 ℃, and the reaction temperature is 100-130 ℃.
With α -Al2O3Or gamma-Al2O3The crystal form is not the best choice, and the invention uses delta-Al2O3The crystal carrier has optimal pore structure and strength without special treatment and simple process. The catalyst obtained under the same conditions has better activity and service life. The proper pore structure of the catalyst is favorable for the diffusion of reactants and products. gamma-Al2O3The crystal form has large specific surface area due to a plurality of small pores, but the pore structure is not beneficial to the diffusion of reactants and products, so the activity is low. Because the skeleton density is low, the carrier strength is poor, and pulverization and inactivation are easy to cause. From delta-Al2O3+α-Al2O3In the mixed crystal form, α -Al appears along with the increase of the calcining temperature and the increase of the calcining time2O3The formation of crystal form, the cumulative pore volume and the specific surface area are reduced, which is also unfavorable for the improvement of the catalyst activity, but the skeleton density is high, and the strength of the catalyst can be properly increased. Two aspects in combination, whereas delta-Al2O3The crystal carrier has proper pore structure and strength, and the prepared catalyst has high activity and long service life.
Drawings
FIG. 1. delta. -Al2O3X-ray diffraction pattern of (a).
Fig. 2 mercury intrusion diagram (a) differential diagram (b) integral diagram.
Detailed Description
Example 1: preparation of delta-Al from pseudo-boehmite2O3And (3) a carrier.
Crushing 320 parts of pseudo-boehmite provided by three petroleum plants#Sieving to obtain powder, adding the powder to obtain powder2 percent of graphite powder with the same mesh number and then 2 percent of CaCO (calcium carbonate) in the weight of the powder3Mixing, adding dilute nitric acid (concentration of 2%) whose powder weight is 45%, stirring uniformly, rolling for several times, extruding out strip-like material whose diameter is 2.5mm by using strip-extruding machine, naturally drying for 4 hr, drying at 120 deg.C, and roasting according to the following heating program. Keeping the temperature at 200 ℃ for 20 minutes, keeping the temperature at 250 ℃ for 20 minutes, keeping the temperature at 300 ℃ for 2 hours, keeping the temperature at 500 ℃ for 30 minutes, keeping the temperature at 600 ℃ for 50 minutes, and keeping the temperature at 900 ℃ for 8 hours. Naturally cooling from 900 deg.C to room temperature.
Example 2: using AlCl3·6H2Preparation of delta-Al from O2O3Carrier
Taking the concentration of 8.5 percent (weight ratio))AlCl3·6H25 parts of O solution and 1 part of 1% NH4OH solution, stirring at 70 deg.C, adding into reactor, adjusting pH to 7-8 with 1% HCl, aging for 30 min, filtering, washing with distilled water until no Cl is detected-Ions are removed. Oven drying at 120 deg.C, pulverizing, and sieving with 320 mesh sieve#Mesh screen, as in example 1, with 1% graphite, 1% CaCO3Mixing, adding 45% dilute nitric acid (concentration of 1%), stirring, grinding, extruding into 2.5mm strips, naturally drying for 6 hr, oven drying at 120 deg.C, and calcining at the following temperature. Keeping the temperature at 200 ℃ for 20 minutes, keeping the temperature at 250 ℃ for 20 minutes, keeping the temperature at 300 ℃ for 2 hours, keeping the temperature at 500 ℃ for 30 minutes, keeping the temperature at 600 ℃ for 50 minutes, and keeping the temperature at 900 ℃ for 8 hours. Naturally cooling from 900 deg.C to room temperature.
Example 3:
preparation of 0.1M FeCl3And (3) solution.
With 1.6657g of PdCl2And 1g of NaCl was added to make 100ml of the solution.
With 1g NaOH and 1.5g NaHCO3To prepare 100ml of mixed alkali liquor.
Taking PdCl25ml of solution, FeCl3Adding 4.7ml of the solution, adding 5ml of distilled water, stirring and mixing, and soaking 5g of gamma-Al2O3And 5 hours, separating and drying the crystal form carrier. Soaking in 5ml mixed alkali solution for 6 hr, filtering, and washing to remove Cl-And (5) drying. With H at 540 deg.C2And changing the original source for 4 hours. Fe. The atomic ratio of Pd is about 1: 1. Obtaining Pd-Fe/gamma-Al2O3A catalyst of the type (I) is provided.
2g of freshly prepared Pd-Fe/gamma-Al from example 32O3Catalyst of type N2The flow rate is 300 ml/min, the activation is carried out for 3 hours at 140 ℃, and the reaction temperature is 110 ℃ and 120 ℃. N is a radical of2The flow rates of CO were 220 ml/min and 130 ml/min, respectively. The ratio of CO to RONO is controlled to be 15-30 to 10-15 (volume ratio). The average yield is 1.22g/1g-1h, the circulation is carried out twice, and the activity is reduced by half in the second circulation.
Example 4
Taking 5 parts of delta-Al2O3Support, 5ml of PdCl prepared in example 3 were added2Solution, immersion for 4 hoursAdding 10ml of mixed alkali liquor, soaking for 5 hours at 70 ℃, filtering and drying. H at 300 DEG C2And reducing for 3 hours. Taking 4.7ml FeCl3Soaking the solution for 4 hours, then soaking the solution for 5 hours by using 5ml of mixed alkali liquor, filtering and washing the solution by water until no Cl is detected-Ions. After drying, H is carried out at 500 DEG C2Reducing for 4 hours to prepare Pd-Fe/delta-Al2O3A two-component catalyst. The atomic ratio of Pd to Fe is about 1: 1.
2g of newly prepared Pd-Fe/delta-Al are taken2O3The catalyst was evaluated under the evaluation conditions of example 3, and the average yield after evaluation was: 1.92g/1g-1 h.
Example 5:
with 3.487g of LaCl3·7H2O, to prepare 100ml LaCl3The aqueous solution of (a) to (b),
PdCl prepared in example 327ml of the solution, taking FeCl32.5ml of the solution, and newly prepared LaCl is taken3Mixing 2.7ml of the solution, adjusting pH to 1.82 to obtain a mixed solution, and soaking 7g of delta-Al2O3+α-Al2O3Mixing crystal form carrier for 5 hr, separating solid, soaking in 8ml mixed alkali solution prepared in 3 for 5 hr, filtering, washing with water until no Cl is detected-And finally, drying. Introducing H at 500 DEG C2Reducing for 4 hours to obtain Pd-Fe-La/delta-Al2O3+α-Al2O3Three-component catalyst. The atomic ratio of La, Fe and Pd is about 1: 2.5.
Taking newly prepared Pd-Fe-La/delta-Al2O3+α-Al2O3Three component catalyst 2 grams, the catalyst was evaluated using the evaluation conditions of example 3. The average yield after evaluation was: 2.33g/1g-1h, the activity is slightly reduced after 3 times of circulation.
Example 6:
taking PdCl27ml of the solution, taking FeCl32.5ml of the solution, and LaCl was taken3Mixing 2.7ml of the solution, adjusting pH to 1.82 to obtain a mixed solution, and soaking 7g of delta-Al2O3And (3) soaking the crystal form carrier for 6 hours. After drying, 10ml of mixed alkali liquor prepared in example 3 is taken and soaked for 4 hours at 70 ℃ and thenFiltering, washing with water until no Cl is detected-. H at 500 DEG C2Reducing for 4 hours to obtain Pd-Fe-La/delta-Al2O3The catalyst has an atomic ratio of La, Fe and Pd of about 1: 2.5.
Taking newly prepared Pd-Fe-La/delta-Al2O32g of type catalyst, evaluation conditions were the same as in example 3, and average yield after evaluation: 3.29g/1g-1h, circulating for 3 times, and gradually increasing the activity.
Claims (8)
1. A catalyst for synthesizing oxalate is characterized by that it is delta-Al2O3As carrier, Pd, Fe and La are loaded.
2. The catalyst for synthesizing oxalate according to claim 1, characterized in that the atomic ratio of the active ingredients Pd, Fe and La is 3-0.5: 2-0.5, respectively.
3. The catalyst for synthesizing oxalate according to claim 1, wherein said delta-Al is2O3The pore structure of the carrier is: total pore volume (ml/g) 0.4-0.9; total pore surface area (m)2Per g)60 to 100; average pore diameter (mum) of 0.03-0.05; apparent density (g/ml) 0.77-1.2; the skeleton density (g/ml) is 2.5-3.5.
4. The method for preparing a catalyst for synthesizing oxalate according to claim 1, comprising the steps of:
1) preparing a steeping fluid by using salts of Pd, Fe and La according to the dosage, wherein the PH value is 1-4.5;
2) beta-Al2O3Addinginto the steeping liquor, and soaking for 2-8 hours;
3) separating, oven drying, soaking in mixed alkaline solution at 70 deg.C for 4-6 hr, washing to remove negative ions,
4) drying, and treating with H at 550 ℃ under 220-2Reducing for 3-5 hours.
5. Use according to claim 1 for closingOxalate-forming catalyst, characterized in that said delta-Al2O3The preparation method of the carrier comprises the following steps:
1) preparation of delta-Al from pseudo-boehmite2O3Carrier
Crushing pseudo-boehmite by 200-400#Sieving with a sieve, adding graphite powder 1-3% of the powder and CaCO 1-3%3Then adding dilute HNO accounting for 45 percent of the powder amount3(the concentration is 1-3%), stirring evenly, rolling, extruding a strip body with the diameter of 2.5mm by a strip extruding machine, drying naturally for 4 hours, drying at 120 ℃, and roasting according to a temperature rising program; naturally cooling to room temperature;
2) from AlCl3·6H2Preparation of delta-Al from O2O3Carrier
5 portions of AlCl with the concentration of 8.6 percent3·6H2O solution and 1 part of NH with the concentration of 1 percent4OH solution reaction, stirring at 70 deg.C, pH 7-8, standing for 30 min, suction filtering, washing with water until no Cl is detected-Drying at 120 deg.C, adding graphite and CaCO in sequence according to the proportion of (1)3Rolling and pressing the mixture into cylindrical thin strips with the diameter of 2.5mm, naturally drying the thin strips for 5 hours, drying the thin strips at 120 ℃ and roasting the thin strips according to the program; naturally cooling to room temperature.
6. The oxalate-synthesizing catalyst carrier according to claim 5, delta-Al2O3The preparation method is characterized in that the AlCl is adopted3·6H2O may be Al2(SO4)3·6H2O or Al (NO)3)3·6H2And O is replaced.
7. The oxalate-synthesizing catalyst carrier according to claim 5, delta-Al2O3The preparation method is characterized in that the roasting temperature-rising program is as follows:
keeping the temperature at 200 ℃ for 20-40 min, keeping the temperature at 250 ℃ for 20-35 min, keeping the temperature at 300 ℃ for 2-4 h
Keeping the temperature at 500 ℃ for 20-40 min, keeping the temperature at 600 ℃ for 20-50 min, and keeping the temperature at 900 ℃ for 4-9 h.
8. The method for using the catalyst for synthesizing oxalate according to claim 1, characterized in that it comprises the following steps: a fixed bed device is adopted, and a reaction tube has a jacket structure. The ratio of CO to RONO is controlled to be 15-30 to 10-15 (volume ratio), the contact time is 0.5-3 seconds, the activation temperature of the catalyst is 120-140 ℃, and the reaction temperature is 100-130 ℃.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101596455B (en) * | 2008-06-04 | 2011-09-07 | 中国石油天然气股份有限公司 | Catalyst for synthesizing oxalate and preparation method thereof |
CN102649729A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for producing oxalate through CO gas phase coupled catalytic reaction |
CN103962130A (en) * | 2014-04-28 | 2014-08-06 | 河南能源化工集团研究院有限公司 | Catalyst for oxalate ester synthetic reaction and preparation method of catalyst |
CN108855024A (en) * | 2018-05-28 | 2018-11-23 | 中化泉州石化有限公司 | A kind of large aperture, high mechanical strength alumina support preparation method |
-
2002
- 2002-10-31 CN CNB021461058A patent/CN1150992C/en not_active Expired - Fee Related
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101596455B (en) * | 2008-06-04 | 2011-09-07 | 中国石油天然气股份有限公司 | Catalyst for synthesizing oxalate and preparation method thereof |
CN102649729A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for producing oxalate through CO gas phase coupled catalytic reaction |
CN103962130A (en) * | 2014-04-28 | 2014-08-06 | 河南能源化工集团研究院有限公司 | Catalyst for oxalate ester synthetic reaction and preparation method of catalyst |
CN103962130B (en) * | 2014-04-28 | 2016-04-06 | 河南能源化工集团研究院有限公司 | A kind of Catalysts and its preparation method for oxalate synthetic reaction |
CN108855024A (en) * | 2018-05-28 | 2018-11-23 | 中化泉州石化有限公司 | A kind of large aperture, high mechanical strength alumina support preparation method |
CN108855024B (en) * | 2018-05-28 | 2021-04-27 | 中化泉州石化有限公司 | Preparation method of alumina carrier with large aperture and high mechanical strength |
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