CN109569628A - For efficiently producing the preparation method of the catalyst of neopentyl glycol and the preparation method of neopentyl glycol - Google Patents
For efficiently producing the preparation method of the catalyst of neopentyl glycol and the preparation method of neopentyl glycol Download PDFInfo
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- CN109569628A CN109569628A CN201811560091.9A CN201811560091A CN109569628A CN 109569628 A CN109569628 A CN 109569628A CN 201811560091 A CN201811560091 A CN 201811560091A CN 109569628 A CN109569628 A CN 109569628A
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- neopentyl glycol
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The process of the invention discloses a kind of in adding a hydrogen fixed bed step continuous production neopentyl glycol, process characteristic are as follows: (1) preparation is with γ-Al2O3For molecular sieve as catalyst carrier, the carrier is cheap, low in cost.(2) catalyst is by cerous nitrate and six nitric hydrate copper and γ-Al2O3Molecular sieve is combined via water bath heating.Metallic cerium, the distinctive anti-carbon of cerium, so that active higher, the longer life expectancy of gained catalyst is added.(3) catalyst is handled, is placed in fixed bed, adjust reaction condition, carried out hydrogenation reaction, obtain optimised process.The conversion ratio of HPA 98%~100%, NPG selectivity 95%~99% or so.
Description
Technical field
The present invention relates to a kind of production new techniques for producing neopentyl glycol, especially Ce-Cu/ γ-Al used2O3Catalysis
The preparation method of agent and its neopentyl glycol is efficiently produced under hydroconversion condition.
Background technique
Neopentyl glycol is that one kind has in chemical industry and medicine and weaving weaving, coating, pesticide and the fields such as automobile and petroleum
Widely applied important industrial chemicals.Since its neopentyl structure is that two primary alconols are in symmetric position, and hydroxyl and
There is no α-hydrogen atom in central carbon atom, so it has very good chemical reactivity, and possesses good thermostabilization
Property and hydrolytic resistance and chemical stability.The polyurethane resin synthesized with neopentyl glycol, the products such as polyurethane have excellent resistance to
Acid-base property, thermal stability, hardness balance and hydrolytic resistance.
NPG- diphenyl may be used as polyethylene terephthalate plasticizer its own (sometimes with other glycol
Mixing) also serve as the thermal stability that additive removes improvement these compounds of polyamide and polyvinyl chloride and chloridized polyolefin.So
After can be used by methylene diisocyanate, the ethylene amino of hydroxyalkyl methacrylate and neopentyl glycol (NPG) synthesis
Ethyl formate is as galley.NPG itself may be used as substitute of the 1,4-butanediol as complexing agent, valuable synthesis profit
Lubricating oil is containing acid group > C6NPG chelating object；And thickening of lubricating oils agent can be carried on a shoulder pole by NPG and other glycol or alkylated NPG
When.It can be as epoxy resin by urea-carbamate compounds that the conversion of NPG and diisocyanate and secondary amine is formed
Curing agent and cigaratte filter adhesive.In fragrance and field of perfumery, NPG is preparing corresponding alcohol ester and cyclic annular contracting
There is extraordinary result in terms of aldehyde or ketal.As detergent and the viscosity modifier of scavenger suspension, or makeup
Product fire retardant, the production and extraction of adhesive tape, distillation auxiliary agent and catalyst etc..NPG is also an option that conversion becomes ketal, is used for
Produce brufen.
Patent CN105175228A calcium legal system neopentyl glycol, uses isobutylaldehyde, formaldehyde for raw material, is catalysis with calcium hydroxide
Agent prepares neopentyl glycol by condensation, evaporation, distillation process.This reaction process is complicated for operation, calcium formate, sodium formate side reaction
Product surcharge is lower, and the consumption of raw material is larger.The method of patent CN108623437A continuous production neopentyl glycol, adds hydrogen
Reaction is proceeded in two phases, and first will be condensed into 3-hydroxypivalic acid neopentyl glycol single by Tishchenko reaction under the action of basic catalyst
Rouge mixed liquor, then 3-hydroxypivalic acid neopentyl glycol monoester mixed liquor is continuously added to time containing hydrogenation catalyst and neopentyl glycol
Hydrogenation reaction is carried out in the reactor of road, reaction product is separated by cross-flow filter, and the circulation fluid containing catalyst is back to back
In the reactor of road, isolated clear liquid carries out rectifying again, obtains neopentyl glycol.This reaction process is complicated for operation, complex steps,
Stepwise reaction condition is difficult to control.
The present invention prepares new catalyst Ce-Cu/ γ-Al by simple water-bath2O3.Because Ce has certain
Anti-carbon prevents catalyst from talking at high temperature, extends the service life of catalyst, while improving the conversion ratio of raw material.This
Kind composite material and preparation method thereof is simple, and condition is easy to control, and low in cost, catalyst activity is relatively high, and service life is longer, institute
With Ce-Cu/ γ-Al2O3Catalyst has great application prospect in neopentyl glycol production field.
Summary of the invention
Technical problem: the present invention provides a kind of processes of continuous production neopentyl glycol in adding hydrogen fixed bed, should
The preparation method of catalyst is relatively simple, and cost is relatively low and can be used for a long time.
Technical solution: a kind of preparation method of effective catalyst of the invention includes the following steps:
(1) modified γ-Al is prepared2O3Catalyst, the catalyst is by cerous nitrate and six nitric hydrate copper and γ-Al2O3Molecule
Sieve is combined via water bath heating.Steps are as follows: by γ-Al2O3It is mixed in distilled water, while stirring at a certain temperature
Cerous nitrate solution and six nitric hydrate copper solutions are added dropwise respectively, washing catalyst to neutrality, filtration drying must urge after mixing evenly
Agent Ce-Cu/ γ-Al2O3。
(2) in fixed bed, hydrogenating reduction 3-4h is carried out to catalyst at pure hydrogen state, 300 DEG C.
(3) reaction condition is adjusted, hydrogenation reaction is carried out, obtains optimised process.
Technical effect: compared with the prior art, the invention has the following advantages:
1, the novel Ce-Cu/ γ-Al of the first public one kind of the present invention2O3The preparation method of catalyst, the catalyst preparation
Method is simple, and condition is easy to control, and catalytic activity is high, and the service life is long, at low cost.
2, the Ce-Cu/ γ-Al prepared by the present invention2O3Catalyst can be can be carried out continuous by applying in fixed bed
Production, and the yield of neopentyl glycol is higher.
Detailed description of the invention
Fig. 1 is 3%Ce-15%Cu/ γ-Al2O3The continuous lab scale of catalyst, the conversion ratio of hydroxy pivalin aldehyde (HPA) and new
The selective figure of pentanediol.
Specific embodiment
Technical solution of the present invention is described in further detail below by example.
Embodiment 1
Ce-Cu/γ-Al2O3Preparation: weigh 10g γ-Al2O3It is placed in baking oven, the pre- place of 2h is carried out at 120 DEG C
Reason.By processed 10g γ-Al2O3It is placed in three-necked flask, is dissolved and stirred with distilled water, sequentially added weighed
Six nitric hydrate copper distilled water solution of 6.87g and 0.406g cerous nitrate distilled water solution.Carbon when heating water bath is stirred to 60 DEG C
Acid sodium solution adjusts PH to 8, and when being heated to 70 DEG C, reaction 3h closes blender, continuous heating aging 2h.Reaction is completed to catalysis
Agent carries out filtering and washing and roasts 3h under 400 degrees Celsius after drying grinding to neutrality, then carries out tabletting.With this condition, HPA
Conversion ratio 95.63%, NPG selectivity 94.87%.
Embodiment 2
Ce-Cu/γ-Al2O3Preparation: weigh 10g γ-Al2O3It is placed in baking oven, the pre- place of 2h is carried out at 120 DEG C
Reason.By processed 10g γ-Al2O3It is placed in three-necked flask, is dissolved and stirred with distilled water, sequentially added weighed
Six nitric hydrate copper distilled water solution of 6.97g and 1.13g cerous nitrate distilled water solution.Carbonic acid when heating water bath is stirred to 60 DEG C
Sodium solution adjusts PH to 8, and when being heated to 70 DEG C, reaction 3h closes blender, continuous heating aging 2h.Reaction is completed to catalyst
It carries out filtering and washing and roasts 3h under 400 degrees Celsius after drying grinding to neutrality, then carry out tabletting.With this condition, HPA
Conversion ratio 100%, NPG selectivity 99.12%.
Embodiment 3
Ce-Cu/γ-Al2O3Preparation: weigh 10g γ-Al2O3It is placed in baking oven, the pre- place of 2h is carried out at 120 DEG C
Reason.By processed 10g γ-Al2O3It is placed in three-necked flask, is dissolved and stirred with distilled water, sequentially added weighed
Six nitric hydrate copper distilled water solution of 7.08g and 1.93g cerous nitrate distilled water solution.Carbonic acid when heating water bath is stirred to 60 DEG C
Sodium solution adjusts PH to 8, and when being heated to 70 DEG C, reaction 3h closes blender, continuous heating aging 2h.Reaction is completed to catalyst
It carries out filtering and washing and roasts 3h under 400 degrees Celsius after drying grinding to neutrality, then carry out tabletting.With this condition, HPA
Conversion ratio 100%, NPG selectivity 96.67%.
Embodiment 4
The preparation of neopentyl glycol: selection 100ml hydroxy pivalin aldehyde (HPA) liquid is raw material, loads 6ml in the reactor and urges
Agent (20-40 mesh), and weighted BMO spaces are carried out to catalyst, 150 DEG C of holding 2h are risen to by room temperature, are then to slowly warm up to
250 DEG C, and keep 250 DEG C of reduction 8h.The parameter of fixed bed is set, and reaction pressure 2Mpa, 115 DEG C of reaction temperature, hydrogen-aldehyde rate are
10 and liquid hourly space velocity (LHSV) 0.1-1h-1。
Embodiment 5
The continuous type lab scale of neopentyl glycol production is carried out with this catalyst, reacts 600h, during the reaction every the left side 30h
Right sampling is detected with gas chromatograph (GC 2010), calculates the conversion ratio of HPA and the selectivity of NPG.
Calculate the conversion ratio of HPA and the selectivity of NPG, the method is as follows:
In formula, M1、M2The respectively relative molecular mass of HPA, NPG.
Claims (3)
1. a kind of, it is characterised in that: described method includes following steps:
(1) γ-Al modified using sluggish precipitation preparation2O3Catalyst weighs a certain amount of 5-8g copper nitrate and 0.1-3g nitre
5-15g γ-Al is added in acid2O3In, be added 50-100ml deionized water be stirred well to it is uniformly mixed, in a water bath by mixed liquor
60~80 DEG C are heated to, starts that precipitating reagent Na is added dropwise2CO3Solution to system pH value 8；It is constant that maintaining reaction temperature is added dropwise
And accelerate 0.5~2h of stirring, then stop stirring, and 4~8h is aged at 60 DEG C；
(2) filtering and washing being carried out to ageing rear catalyst, the catalyst of drying is milled into powder by 80~120 DEG C of drying, 400~
600 DEG C roast 4~6h in Muffle furnace；
(3) catalyst is finally subjected to tabletting cutting sieving, selects 20~40 mesh particles as efficiently producing neopentyl glycol
Cu/ γ-Al2O3Catalyst.
2. according to described in claim 1 for efficiently producing the Cu/ γ-Al of neopentyl glycol2O3The preparation method of catalyst, catalysis
Agent cerium-oxide contents aoxidize copper content in 15-20wt%, aluminium oxide is in 70-80wt% in 1-5wt%.
3. a kind of method of efficiently production neopentyl glycol, it is characterised in that: the described method includes:
With (20-100%) HPA ethanol solution in adding hydrogen fixed bed, parameter is set are as follows: 1~3Mpa of reaction pressure or so, reaction
95~150 DEG C of temperature, hydrogen-aldehyde rate are >=10 and liquid hourly space velocity (LHSV) 0.1-1h-1Under conditions of.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294570A (en) * | 1998-03-05 | 2001-05-09 | 巴斯福股份公司 | Method for hydrogenating carbonyl compounds |
| WO2009079826A1 (en) * | 2007-12-14 | 2009-07-02 | Wanthane Polymers Co., Ltd. | Thermoplastic polyurethane elastomer with hydrolytic stability and preparing method thereof |
| CN104857965A (en) * | 2015-05-28 | 2015-08-26 | 常州大学 | Preparation method and application process of catalyst for producing hydrogen by methanol steam reformation |
| CN106669731A (en) * | 2015-11-09 | 2017-05-17 | 万华化学集团股份有限公司 | Catalyst applied to amination of polyether polyol, preparation method thereof and method for preparing polyether amine by using catalyst |
| CN107983356A (en) * | 2017-12-07 | 2018-05-04 | 中国科学院山西煤炭化学研究所 | A kind of catalyst and preparation method and application for synthesizing higher order branched alcohol |
-
2018
- 2018-12-20 CN CN201811560091.9A patent/CN109569628A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294570A (en) * | 1998-03-05 | 2001-05-09 | 巴斯福股份公司 | Method for hydrogenating carbonyl compounds |
| WO2009079826A1 (en) * | 2007-12-14 | 2009-07-02 | Wanthane Polymers Co., Ltd. | Thermoplastic polyurethane elastomer with hydrolytic stability and preparing method thereof |
| CN104857965A (en) * | 2015-05-28 | 2015-08-26 | 常州大学 | Preparation method and application process of catalyst for producing hydrogen by methanol steam reformation |
| CN106669731A (en) * | 2015-11-09 | 2017-05-17 | 万华化学集团股份有限公司 | Catalyst applied to amination of polyether polyol, preparation method thereof and method for preparing polyether amine by using catalyst |
| CN107983356A (en) * | 2017-12-07 | 2018-05-04 | 中国科学院山西煤炭化学研究所 | A kind of catalyst and preparation method and application for synthesizing higher order branched alcohol |
Non-Patent Citations (1)
| Title |
|---|
| 张冬梅，: ""羟基新戊醛加氢制备新戊二醇催化剂及其工艺研究"", 《万方学位论文数据库》 * |
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Application publication date: 20190405 |