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CN1162385C - Dibasic carboxylic acid ester hydrogenation catalyst and its preparation and application - Google Patents

Dibasic carboxylic acid ester hydrogenation catalyst and its preparation and application Download PDF

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Publication number
CN1162385C
CN1162385C CNB011198095A CN01119809A CN1162385C CN 1162385 C CN1162385 C CN 1162385C CN B011198095 A CNB011198095 A CN B011198095A CN 01119809 A CN01119809 A CN 01119809A CN 1162385 C CN1162385 C CN 1162385C
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ester
catalyst
preparation
dialkyl
catalyzer
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CN1393433A (en
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王海京
张建国
高国强
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to a catalyst for preparing dihydric alcohol by the hydrogenation of dicarboxylic acid ester. The catalyst has the following general formula: CuMn [a]Al [b]O[c], wherein a=0.05 to 3; b=0.05 to 7; b>/=a; c is oxygen atomicity which satisfies the requirement of metallic element valence. The catalyst does not contain chromium as a toxic component and is favorable to environmental protection. Compared with the existing catalyst containing chromium, the catalyst has the advantages of high activity, stability and selectivity of the dibasic alcohol.

Description

Dicarboxylic esters hydrogenation catalyst and preparation thereof and application
The present invention relates to a kind of catalyzer that is used for dicarboxylic esters hydrogenation preparing dibasic alcohol.
The dibasic alcohol of industrial widespread use mainly contains 1,4-butyleneglycol and 1, ammediol etc., they all are important Organic Chemicals, wherein 1, ammediol can be used as the raw material of spandex fiber, 1, the 4-butyleneglycol is mainly used in production polybutyl terapthalate (PBT), urethane, gamma-butyrolactone and tetrahydrofuran (THF) etc.
In the prior art 1, the preparation method of ammediol generates hydroxy propanal by oxyethane through hydroformylation, 3-hydroxyl propionaldehyde hydrogenation to produce is got again.Do not see the report that makes propylene glycol by the dialkyl malonate hydrogenation.
Common 1, the 4-butyleneglycol is to be raw material with acetylene and formaldehyde, and is under high pressure synthetic, also can make by the gamma-butyrolactone hydrogenation or by the tetrahydrofuran (THF) hydrolysis.The development for preparing the MALEIC ANHYDRIDE technology along with butane oxidation, make 1 from the maleate vapour phase hydrogenation, the method development of 4-butyleneglycol is very fast, disclosing a kind of as EP 143634 is catalyzer with the Cu-Cr-Mn-Ba mixed oxide, with the maleate is raw material, adopt two sections vapour phase hydrogenation manufactured 1, the method for 4-butyleneglycol.It is catalyzer with the Cu-Zn-Cr-Zr mixed oxide that CN 1046216C discloses a kind of, is raw material with MALEIC ANHYDRIDE or maleate, adopts one section vapour phase hydrogenation manufactured 1, the method for 4-butyleneglycol.
Though the catalyzer that uses in the above prior art has higher activity and selectivity, all contain chromium.As everyone knows, chromium is the metal that a kind of toxicity is big, contaminative is strong, causes very big harm can for generation personnel and environment; In order to eliminate pollution of chromium, must drop into substantial contribution and protect and administer, therefore, chromium-containing catalyst does not meet economy and environmental protection demand for development.
The purpose of this invention is to provide a kind of hydrogenation catalyst that does not contain chromium with higher activity, selectivity and satisfactory stability.
Another object of the present invention provides above-mentioned Preparation of catalysts method.
A further object of the present invention provides the method that above-mentioned catalyzer is used for dicarboxylic esters hydrogenation preparing dibasic alcohol.
The composite oxides that catalyzer provided by the invention is made up of Cu, Mn, Al, this catalyzer has following general formula: CuMn aAl bO c, a=0.05～3 wherein, preferred 0.15～2.5, more preferably 0.7～1; B=0.05～7, preferred 0.4～5, more preferably 2～4, and b 〉=a; C is the oxygen atomicity that satisfies each metallic element valency requirement.
Catalyzer provided by the invention adopts the method preparation of co-precipitation: the soluble salt of Cu, Mn, Al is dissolved in the deionized water, at 15～70 ℃, under preferred 20～50 ℃ with alkali precipitation to pH=4～11, aging 0.5～5.0 hour, filter then, washing, collecting precipitation, in 70～200 ℃ of dryings 2～30 hours, in 300～900 ℃ of roastings 2～30 hours, promptly get catalyzer of the present invention again.Wherein soluble salt solution can be the solution that contains Cu, Mn, three kinds of metal-salts of Al simultaneously, also can be only to contain the wherein solution of one or both metal-salts, if the latter, can earlier several solution that contain different metal salt be used alkali precipitation respectively, again reacted solution be mixed the back and wear out.
The preferred nitrate separately of the soluble salt of described Cu, Mn, Al.
Described alkali can be volatile salt, bicarbonate of ammonia, ammoniacal liquor, yellow soda ash, sodium hydroxide and potassium hydroxide etc., preferred ammoniacal liquor, volatile salt and bicarbonate of ammonia.The concentration of alkali lye is 5～40%, preferred 10～35%.
Catalyzer provided by the invention need carry out prereduction before using, reductive agent can adopt reducing gas such as hydrogen, carbon monoxide, reduction is carried out under 0.1～2.0MPa, 150～300 ℃ of conditions, and the reducing gas flow is 50～500ml/min for every milliliter of catalyzer.
Catalyzer of the present invention is applicable to the dicarboxylic esters hydrogenation preparing dibasic alcohol of carbon number≤6, and said dicarboxylic esters comprises dialkyl maleate, dialkyl malonate, dialkyl succinate, dialkyl fumarate etc.Alkyl wherein is C 1～C 6Alkyl, preferable methyl, ethyl and butyl.Hydrogenation reaction adopts single hop fixed bed mode to carry out, and temperature of reaction is 170～250 ℃, and preferred 180～220 ℃, pressure is 2.5～7.0MPa, preferred 3.0～6.5MPa, and the air speed of ester is 0.1～2.0hr -1, preferred 0.2～1.5hr -1, the mol ratio of hydrogen/ester is 250～700: 1, preferred 250～600: 1.
Catalyzer provided by the invention in catalyzer manufacturing and use, makes operator's safety obtain guarantee owing to do not contain the very big chromium component of toxicity, and environment has obtained protection, and has saved the expense that is used for environmental protection in a large number.Catalyzer of the present invention is compared with existing chromium-containing catalyst, has higher activity and dibasic alcohol selectivity.For example, with the dimethyl maleate feedstock production 1, in the reaction of 4-butyleneglycol, at 189 ± 1 ℃, LHSV=1.2hr -1The time, transformation efficiency is 99.8% (mol), 1, and 4-butyleneglycol selectivity can reach 80% (mol).
In addition, catalyzer provided by the invention is in preparation process, adopting ammoniacal liquor, volatile salt or bicarbonate of ammonia is precipitation agent, the consumption of washing water in the time of can significantly reducing Preparation of Catalyst, reduce washing times, improve the production efficiency of catalyzer, and prepared catalyzer have better choice, activity and stable.
Further specify characteristics of the present invention below by embodiment.
Embodiment 1～5 is a Preparation of catalysts.
Embodiment 1
With 52.2g Cu (NO 3) 23H 2O (Beijing Chemical Plant's product, chemical pure), 17g 50%Mn (NO 3) 2The aqueous solution (Beijing Chemical Plant's product, chemical pure), 32.9g Al (NO 3) 39H 2O (Beijing Chemical Plant's product, chemical pure) is dissolved in the 400ml deionized water, stir down at 50 ± 1 ℃, drip 20wt% ammoniacal liquor (Beijing Chemical Plant's product, chemical pure), until the pH of solution is 6.0 ± 0.5, aging 1 hour, to filter then, washing is once, collecting precipitation, 200 ℃ of dry 2hr, 800 ± 10 ℃ of roasting 12hr promptly get catalyst A: CuMn 0.2Al 0.4O 1.9
Embodiment 2
With 52.2g Cu (NO 3) 23H 2O, 81.3g 50%Mn (NO 3) 2The aqueous solution, 81.8gAl (NO 3) 39H 2O is dissolved in the 1000ml deionized water and makes solution A, with Na 2CO 3(15wt%) wiring solution-forming B, the 200ml deionized water of in the 2000ml beaker, packing into, with A, B solution under 15 ± 1 ℃ of stirrings, add in the beaker simultaneously, control A, B flow velocity make pH remain at 8 ± 0.5, after dripping off, aging 1hr, filter then, through 8 washings, collecting precipitation, at 120 ℃ of dry 2hr, 600 ± 10 ℃ of roasting 24hr, promptly get catalyst B: CuMnAlO 4
Embodiment 3
With 52.2g Cu (NO 3) 23H 2O, 10.7g 50%Mn (NO 3) 2The aqueous solution, 11.5gAl (NO 3) 39H 2O is dissolved in the 200ml deionized water as solution A, preparation 23wt% ammonium bicarbonate soln is as solution B, at 40 ± 1 ℃ A, B and drip are added, keeping precipitation pH is 5.5 ± 0.5, treat that the A drips of solution adds after, aging 1 hour, filter then, wash once, collecting precipitation, 150 ℃ of dry 2hr, 500 ± 10 ℃ of roasting 24hr promptly get catalyzer C:CuMn 0.09Al 0.14O 1.38
Embodiment 4
With 52.2g Cu (NO 3) 23H 2O, 142g 50%Mn (NO 3) 2The aqueous solution, 225gAl (NO 3) 39H 2O is dissolved in the 700ml deionized water, at room temperature drips 15wt% ammoniacal liquor, is 9.5 ± 0.5 until pH value of solution, and aging 1 hour, filter then, wash once, collecting precipitation, 200 ℃ of dry 2hr, 750 ± 10 ℃ of roasting 18hr promptly get catalyzer D:CuMn 2.3Al 3.4O 9.55
Embodiment 5
With 58g Cu (NO 3) 23H 2O, 122g 50%Mn (NO 3) 2The aqueous solution, 407gAl (NO 3) 39H 2O is dissolved in the 1000ml deionized water, as solution A, the 160g volatile salt is dissolved in the 700ml deionized water as solution B, under 50 ℃ of stirrings, A is splashed among the B, when pH＜6.5, preparation 18wt% ammonium bicarbonate soln, with metal salt solution with and stream mode drip control final solution pH=7.0 ± 0.5, after metal salt solution drips off, aging 1 hour, filter then, wash once, collecting precipitation, 150 ℃ of dry 2hr, 800 ± 10 ℃ of roasting 2hr promptly get catalyzer E:CuMn 1.44Al 4.99O 10.65
Embodiment 6～10 is 1, the preparation of 4-butyleneglycol.
Embodiment 6
Get granularity and be 26～40 order catalyst A 3.2g internal diameter 8mm that packs into, in the tubular reactor that the stainless steel of length 400mm is made, under 200 ℃, 2.0MPa condition with the logical H of flow velocity of 300ml/min 2Reductase 12 0hr then, is that raw material is at 189 ± 1 ℃ of temperature of reaction, pressure 5.8 ± 0.2Mpa, H with the dimethyl maleate 2/ ester 269: 1 (mol), stock liquid hourly space velocity 1.2hr -1React under the condition, products therefrom detects through FID with the gas chromatograph of PEG20000 packed column, the results are shown in Table 1.
Embodiment 7
To react after the method reduction of catalyst B by embodiment 6, different is 200 ± 1 ℃ of temperature of reaction, H 2/ ester is 350: 1mol, liquid hourly space velocity is 0.24hr -1, reaction result sees Table 1.
Embodiment 8
To react after the method reduction of catalyzer C by embodiment 6, different is 189 ± 1 ℃ of temperature of reaction, pressure 5.8 ± 0.2MPa, H 2/ ester is 300: 1 (mol), liquid hourly space velocity 0.6h -1, reaction result sees Table 1.
Embodiment 9
To react after the method reduction of catalyzer D by embodiment 6, different is that temperature of reaction is 200 ± 1 ℃, pressure 3.0 ± 0.2MPa, H 2/ ester is 239 ± 10: 1 (mol), liquid hourly space velocity 0.6h -1Reaction result sees Table 1.
Embodiment 10
To react after the method reduction of catalyzer E by embodiment 6, different is that temperature of reaction is 192 ± 2 ℃, pressure 5.8 ± 0.2MPa, H 2/ ester is 250: 1 (mol), liquid hourly space velocity 0.36h -1, the operation continuously through 1500 hours, active, selectivity is not seen considerable change, reaction result sees Table 1.
Embodiment 11 and 12 is 1, the preparation of ammediol.
Embodiment 11
With reacting after the method reduction of catalyzer D by embodiment 6, with the diethyl malonate raw material, at 185 ± 1 ℃ of temperature of reaction, pressure 6.7 ± 0.2Mpa, H 2/ ester 600: 1 (mol), stock liquid hourly space velocity 0.24hr -1Under the condition, the transformation efficiency of diethyl malonate is 99mol%, 1, and the selectivity 70mol% of ammediol.
Embodiment 12
With reacting after the method reduction of catalyzer C by embodiment 6, with the diethyl malonate raw material, at 192 ± 2 ℃ of temperature of reaction, pressure 5.8 ± 0.2Mpa, H 2/ ester 400: 1 (mol), stock liquid hourly space velocity 0.24hr -1Under the condition, the transformation efficiency of diethyl malonate is 98.5mol%, 1, and the selectivity 63.9mol% of ammediol.
Table 1
Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10
The catalyzer numbering A B C D E
Temperature of reaction (℃) 189±1 200±1 189±1 200±1 192±2
Reaction pressure (MPa) 5.8±0.2 5.8±0.2 5.8±0.2 3.0±0.2 5.8±0.2
H 2/ ester (mol) 269 350 300 239±10 250
Ester liquid hourly space velocity (hr -1) 1.2 0.24 0.6 0.6 0.36
Ester conversion rate mol% 99.8 70 100 100 99.5
Selectivity mol% 1, the 4-butyleneglycol 80 67.3 80.6 55.2 81.2
Gamma-butyrolactone 16 12.6 14.2 37.7 14.2
Tetrahydrofuran (THF) 2.9 9.1 3.6 5.3 2.2
Butanols 1.1 10.1 1.6 1.8 2.4

Claims (10)

1.一种用于二元羧酸酯加氢制备二元醇的催化剂，具有以下通式：CuMnaAlbOc，其中a＝0.05～3，b＝0.05～7，且b≥a，c为满足各金属元素化合价要求的氧原子数。1. A catalyst for the preparation of dibasic alcohols by hydrogenation of dibasic carboxylic acid esters has the following general formula: CuMn a Al b O c , wherein a=0.05～3, b=0.05～7, and b≥a, c is the number of oxygen atoms meeting the valence requirements of each metal element. 2.按照权利要求1所述的催化剂，其特征在于，其中a＝0.15～2.5，b＝0.4～5。2. The catalyst according to claim 1, wherein a=0.15-2.5, b=0.4-5. 3.按照权利要求1或2所述的催化剂，其特征在于，其中a＝0.7～1，b＝2～4。3. The catalyst according to claim 1 or 2, wherein a=0.7-1, b=2-4. 4.权利要求1所述催化剂的制备方法，其特征在于，包括：将Cu、Mn、Al的可溶性盐溶于脱离子水中，在15～70℃下用碱沉淀至pH＝4～11，老化0.5～5.0小时，然后过滤、洗涤、收集沉淀，于70～200℃干燥2～30小时，再于300～900℃焙烧2～30小时。4. The preparation method of the catalyst according to claim 1, characterized in that it comprises: dissolving soluble salts of Cu, Mn and Al in deionized water, precipitating with alkali to pH=4～11 at 15～70° C., aging 0.5-5.0 hours, then filter, wash, collect the precipitate, dry at 70-200°C for 2-30 hours, and then roast at 300-900°C for 2-30 hours. 5.按照权利要求4所述的制备方法，其特征在于，所说Cu、Mn、Al的可溶性盐为各自的硝酸盐。5. according to the described preparation method of claim 4, it is characterized in that, the soluble salt of said Cu, Mn, Al is respective nitrate. 6.按照权利要求4所述的制备方法，其特征在于，所述的碱选自碳酸铵、碳酸氢铵、氨水、碳酸钠、氢氧化钠和氢氧化钾，碱液的浓度为5～40％。6. according to the described preparation method of claim 4, it is characterized in that, described alkali is selected from ammonium carbonate, ammonium bicarbonate, ammoniacal liquor, sodium carbonate, sodium hydroxide and potassium hydroxide, and the concentration of lye is 5～40 %. 7.按照权利要求4或6所述的制备方法，其特征在于，所述的碱选自氨水、碳酸铵和碳酸氢铵，碱液的浓度为10～35％。7. according to the described preparation method of claim 4 or 6, it is characterized in that, described alkali is selected from ammonia water, ammonium carbonate and ammonium bicarbonate, and the concentration of lye is 10～35%. 8.权利要求1所述催化剂的应用方法，其特征在于，使碳数≤6的二元羧酸酯与权利要求1所述的催化剂接触，在反应温度为170～250℃，压力为2.5～7.0MPa，酯的空速为0.1～2.0hr-1，氢气/酯的摩尔比为250～700∶1的条件下进行反应，收集二元醇。8. The application method of the catalyst according to claim 1, characterized in that, the dicarboxylic acid ester with carbon number≤6 is contacted with the catalyst according to claim 1, and the reaction temperature is 170～250° C., and the pressure is 2.5～ The reaction is carried out under the conditions of 7.0 MPa, the space velocity of the ester is 0.1-2.0 hr -1 , and the molar ratio of hydrogen/ester is 250-700:1, and the glycol is collected. 9.按照权利要求8所述的应用方法，其特征在于，所说二元羧酸酯选自马来酸二烷基酯，丙二酸二烷基酯，琥珀酸二烷基酯，富马酸二烷基酯，其中的烷基为C1～C6烷基。9. according to the described application method of claim 8, it is characterized in that, said dibasic carboxylic acid ester is selected from dialkyl maleate, dialkyl malonate, dialkyl succinate, fumarate Acid dialkyl ester, wherein the alkyl is C 1 ~C 6 alkyl. 10.按照权利要求8所述的应用方法，其特征在于，反应温度为180～220℃，压力为3.0～6.5MPa，酯的空速为0.2～1.5hr-1，氢气/酯的摩尔比为250～600∶1。10. The application method according to claim 8, characterized in that the reaction temperature is 180-220°C, the pressure is 3.0-6.5MPa, the space velocity of the ester is 0.2-1.5hr -1 , and the molar ratio of hydrogen/ester is 250～600:1.
CNB011198095A 2001-06-29 2001-06-29 Dibasic carboxylic acid ester hydrogenation catalyst and its preparation and application Expired - Lifetime CN1162385C (en)

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CN103100394B (en) * 2011-11-09 2014-07-23 中国石油化工股份有限公司 Preparation method of hydrogenation catalyst
CN106336345B (en) * 2015-07-10 2019-11-22 华东理工大学 Process for the preparation of 1,3-propanediol
CN105435791B (en) * 2015-12-03 2021-08-10 上海华谊能源化工有限公司 Catalyst for preparing 1, 3-propanediol by hydrogenating dialkyl malonate and preparation method and application thereof

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