CN1162385C - Hydrocatalyst of binary carboxylate and its preparing process and application - Google Patents
Hydrocatalyst of binary carboxylate and its preparing process and application Download PDFInfo
- 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
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- ester
- catalyst
- alkali
- dialkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- 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
Landscapes
- 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
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. a catalyzer that is used for dicarboxylic esters hydrogenation preparing dibasic alcohol has following general formula: CuMn
aAl
bO
c, a=0.05～3 wherein, b=0.05～7, and b 〉=a, c is the oxygen atomicity that satisfies each metallic element valency requirement.
2. according to the described catalyzer of claim 1, it is characterized in that a=0.15～2.5 wherein, b=0.4～5.
3. according to claim 1 or 2 described catalyzer, it is characterized in that a=0.7～1 wherein, b=2～4.
4. the described Preparation of catalysts method of claim 1, it is characterized in that, comprise: the soluble salt of Cu, Mn, Al is dissolved in the deionized water, under 15～70 ℃ 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, again in 300～900 ℃ of roastings 2～30 hours.
5. according to the described preparation method of claim 4, it is characterized in that the soluble salt of said Cu, Mn, Al is a nitrate separately.
6. according to the described preparation method of claim 4, it is characterized in that described alkali is selected from volatile salt, bicarbonate of ammonia, ammoniacal liquor, yellow soda ash, sodium hydroxide and potassium hydroxide, the concentration of alkali lye is 5～40%.
7. according to claim 4 or 6 described preparation methods, it is characterized in that described alkali is selected from ammoniacal liquor, volatile salt and bicarbonate of ammonia, the concentration of alkali lye is 10～35%.
8. the described Application of Catalyst method of claim 1 is characterized in that, the dicarboxylic esters of carbon number≤6 is contacted with the described catalyzer of claim 1, is 170～250 ℃ in temperature of reaction, and pressure is 2.5～7.0MPa, and the air speed of ester is 0.1～2.0hr
-1, the mol ratio of hydrogen/ester is to react under 250～700: 1 the condition, collects dibasic alcohol.
9. according to the described application method of claim 8, it is characterized in that said dicarboxylic esters is selected from dialkyl maleate, dialkyl malonate, dialkyl succinate, dialkyl fumarate, alkyl wherein are C
1～C
6Alkyl.
10. according to the described application method of claim 8, it is characterized in that temperature of reaction is 180～220 ℃, pressure is 3.0～6.5MPa, and the air speed of ester is 0.2～1.5hr
-1, the mol ratio of hydrogen/ester is 250～600: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011198095A CN1162385C (en) | 2001-06-29 | 2001-06-29 | Hydrocatalyst of binary carboxylate and its preparing process and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011198095A CN1162385C (en) | 2001-06-29 | 2001-06-29 | Hydrocatalyst of binary carboxylate and its preparing process and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1393433A CN1393433A (en) | 2003-01-29 |
| CN1162385C true CN1162385C (en) | 2004-08-18 |
Family
ID=4663725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011198095A Expired - Lifetime CN1162385C (en) | 2001-06-29 | 2001-06-29 | Hydrocatalyst of binary carboxylate and its preparing process and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1162385C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 | The method for preparing 1,3- propylene glycol |
| 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 |
-
2001
- 2001-06-29 CN CNB011198095A patent/CN1162385C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1393433A (en) | 2003-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101138730B (en) | Catalyzer for oxalic ester hydrogenation for synthesizing glycolate and method of preparing the same | |
| US4440873A (en) | Process for producing ethylene glycol and/or glycolic acid ester, catalyst composition used therefor, and process for production thereof | |
| CN101020635A (en) | Prepn process of 3-hydroxy propionate and propylene glycol | |
| CN102388009A (en) | Method for producing 1,6-hexanediol | |
| CN1230458A (en) | Catalyst for preparation of ethanol by hydrogenating acetaldehyde, ethyl acetate, acetic acid or their mixture | |
| CN103100393B (en) | Hydrogenation catalyst and preparation method thereof | |
| CN1162385C (en) | Hydrocatalyst of binary carboxylate and its preparing process and application | |
| CN104549318A (en) | Catalyst for preparing furfuryl alcohol through hydrogenating furfural liquid phase and preparation method of catalyst | |
| CN1216877C (en) | Method of preparing gamma-butyrolactone and/or 1,4-butanediol using chromium less catalyst | |
| CN1052663C (en) | Catalyst(A) for preparation of 1,4-butanediol by gas-phase hydrogenation | |
| CN101134713B (en) | Method for preparing 1,3-methyl glycol | |
| CN1072524C (en) | Catalyst for making 1, 4 -butanediol by gas phase hydrogenation | |
| CN1225852A (en) | Dicarbonic oxygen-contained compound catalyst such as alcohols, acetic acid, acetaldehyde etc. made from synthetic gas and process thereof | |
| CN104549320A (en) | Catalyst for preparing furfuryl alcohol by gas-phase hydrogenation of furfuraldehyde and preparation method | |
| CN103769157B (en) | Preparation method of hydrogenation catalyst | |
| CN1052665C (en) | Catalyst for gas-phase dehydrogenation of 1, 4-butanediol to prepare gamma-butyl lactone | |
| CN1257897C (en) | Method of preparing gamma butyrolactone by 1,4-butanediol dehydrogenation | |
| CN112871171A (en) | Preparation method for preparing multi-element low-carbon alcohol by dimethyl oxalate gas-phase hydrogenation | |
| CN101422732A (en) | Catalyst for producing 1,4-butylediol and preparation method and use thereof | |
| CN1117622C (en) | Catalyst for preparing 1,4-butanediol by gas-phase hydrogenation of dialkyl maleate and/or dialkyl succinate | |
| CN1047768C (en) | Method for synthesizing cobalt carbonyl by catalyzing at normal temp. and pressure | |
| CN1049207C (en) | Method for preparing 1,4-butanediol | |
| CN1173779C (en) | Catalyst of cis-anhydride normal pressure hydrogenation preparing gama-butalactone and preparation process | |
| CN1137944A (en) | Catalyst (B) for preparation of 1,4-butanediol by gas-phase hydrogenation | |
| CN1660488A (en) | Preparing catalyst of tetrahydrofuran by adding hydrogen to maleic anhydride in gas phase and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20040818 |