CN1150153C - Catalyst for preparing methoxy acetone and its prepn and application - Google Patents
Catalyst for preparing methoxy acetone and its prepn and application Download PDFInfo
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- CN1150153C CN1150153C CNB011312920A CN01131292A CN1150153C CN 1150153 C CN1150153 C CN 1150153C CN B011312920 A CNB011312920 A CN B011312920A CN 01131292 A CN01131292 A CN 01131292A CN 1150153 C CN1150153 C CN 1150153C
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- carrier
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- catalyst
- oxide compound
- methoxyl group
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Abstract
The present invention relates to a catalyst for preparing methoxyacetone. The main components of the catalyst are metals comprising Cu, Ag , or Mo, etc.; the auxiliary agents mainly contain metals including Mg, Ni , Cr , K, Li , Ce, etc.; the carrier can be silica gel, alumina or molecular sieve, etc. The reaction temperature is generally from 250DEG C to 350DEG C, the carrier gas pressure is one atmospheric pressure, and the space velocity is from 1.4 to 4.2 ml/g. h. 1-methoxy-2-propanol has high conversion rate and favorable selectivity on the catalyst surface so as to create conditions for separating methoxyacetone from the products. The catalyst has the advantages of convenient preparation, long service life and easy regeneration, and can meet the requirements of industrialized production.
Description
Technical field
This patent relates to a kind of 1-of being used for methoxyl group-2-propyl alcohol catalyzed oxidation and prepares the used Catalysts and its preparation method of methoxy propyl reactive ketone.
Background technology
Methoxy acetone is a kind of important chemical product, adopts the method preparation of oxidation 1-methoxyl group-2-propyl alcohol usually.Because the influence of methoxyl group inductive effect, the activity of 1-methoxyl group-2-propyl alcohol is far below other secondary alcohol.The consistence of 1-methoxyl group-2-propyl alcohol and methoxy acetone boiling point also is the where the shoe pinches of synthesizing methoxy acetone simultaneously.
U.S. Pat 3,462,495 disclose a kind of mixture (1-25: 1) pump into reactor after preheating of 1-methoxyl group-2-third alcohol and water.Be filled with the phosphate catalyst of Ca-Ni in the reactor.The transformation efficiency of 1-methoxyl group-2-propyl alcohol is 55% under certain condition.But catalyzer is inactivation very easily, needs regeneration in per 1 hour once.
In addition, document (Heterogeneous Catalysis and Fine Chemicals IV.Dehydrogenation of methoxyisopropanol to methoxyacetone onsupported bimetallic Cu-Zn catalysts, 1997,407.) reported a kind of technology of utilizing above-mentioned prepared in reaction methoxy acetone, be at long 20cm, caliber is filling 5g 8%Cu-10%Zn/Al in the tubular reactor of 10mm
2O
3Catalyzer is done carrier gas with nitrogen, and nebulizer gas pressure is 1 normal atmosphere, and design temperature is 270 degree.In air speed is 7.0h
-1Transformation efficiency about 46.2%, yield 40%.Obviously, the transformation efficiency that how to improve 1-methoxyl group-2-propyl alcohol oxidizing reaction is an industrial urgency problem to be solved.
Summary of the invention
In order to address the above problem, the invention provides a kind of catalyzer that is used to prepare methoxy acetone.Utilize well oxidation 1-methoxyl group-2-propyl alcohol of catalyst system of the present invention, also satisfied simultaneously when separating requirement the methoxy acetone relative content.
Specifically, the invention provides the catalyzer of the oxidative dehydrogenation of a kind of 1-of being used for methoxyl group-2-propyl alcohol, it is characterized in that being represented by formula M N/PZ, wherein: M represents that the activity of such catalysts component is the oxide compound of Cu, Ag or Mo; N represents that promotor is a kind of or two kinds in the oxide compound of Mg, Ni or Cr; P represents that promotor is the oxide compound of Li, K or Ce; Z represents that carrier is a molecular sieve, Al
2O
3Or SiO
2Active ingredient M content is the 5-20% of catalyst weight; Promotor N content is the 0-20% of catalyst weight; Promotor P content is the 0-10% of catalyst weight; All the other are carrier Z.
In above-mentioned catalyzer, preferably M is the oxide compound of Cu, and N is the oxide compound of Ni, and the weight ratio of M: N is 0.5: 1-2.5: 1.
In addition, in above-mentioned catalyzer, preferably P is the oxide compound of K, and the content of P is the 0.5-5% of catalyst weight.
The invention provides the Preparation of catalysts method of the oxidative dehydrogenation of the above-mentioned 1-of being used for methoxyl group-2-propyl alcohol, be to adopt pickling process that active ingredient and cocatalyst component are supported on the carrier, promptly use the solution impregnating carrier Z of the soluble salt of the element that contains active ingredient M and/or cocatalyst component N and P, then after drying, obtain catalyzer in 350-700 ℃ of following roasting.
In above-mentioned preparation method, soluble salt is nitrate, vitriol or the muriate that contains active ingredient M, cocatalyst component N and P.In addition, at first dipping M and/or N component on carrier are flooded the P component after drying again.
The oxidation of 1-methoxyl group provided by the invention-2-propyl alcohol prepares the reaction of methoxy acetone, use the above-mentioned catalyzer of the present invention, reaction conditions is: temperature of reaction is at 250-350 ℃, and air speed is between 1.5-4.3ml/g.h, and flow rate of carrier gas is between 500-2000ml/h.
From the above, because Preparation of Catalyst of the present invention is convenient, the transformation efficiency height of 1-methoxyl group-2-propyl alcohol, the selectivity of methoxy acetone is better, and has the life-span preferably.Active ingredient exists with the state of oxidation in the catalyzer simultaneously, does not need reduction activation, has bigger space-time yield, easily regeneration behind the catalyst deactivation, and active nothing obviously reduces.
Embodiment
Below by example catalyst system is further described.
Example 1 Preparation of catalysts
With carrier Y molecular sieve, beta-molecular sieve, 4A molecular sieve, Al
2O
3Or SiO
2Become 40-60 order particulate state, the nitrate aqueous solution impregnated carrier with containing M and N after 120 ℃ of following dryings, made single component, two-pack or three component catalysts in 5 hours in 550 ℃ of following roastings.Carry out for the dipping of the P component aqueous solution with its nitrate or oxyhydroxide, dipping is after after 120 ℃ of dryings, carry out roasting and obtain catalyzer under 550 ℃.
In following experiment, the catalyzer that catalyst system therefor is all prepared as stated above, the composition of its catalyzer is represented with weight % in each embodiment.In addition, example of the present invention related respond and all in fixed-bed reactor, carry out.The long 20cm of fixed-bed reactor, internal diameter 10mm, thermocouple jack 1mm.General filling 5g catalyzer (about 5-7cm), catalyzer two ends filling inert quartz sand.Carrier gas is an air, and nebulizer gas pressure is 1 normal atmosphere, and flow rate of carrier gas is measured by soap-foam flowmeter.Product receives through condensation.
Example 2
Filling 5g 15%CuO-19.5%NiO/ molecular sieve in reactor, beds two ends filling inert quartz sand.Carrier gas is an air, pressure 1 normal atmosphere.System temperature is set at 300 ℃, and flow rate of carrier gas is adjusted to 1482.5ml/h, air speed 2.4ml/g.h (unit time is by the volume number of unit vol catalyzer).Under this condition 1-methoxyl group-2-propyl alcohol is pumped into reactor after preheating, product is collected in condensation behind catalyst bed reaction.Product is quantitative through the chromatography-mass spectroscopy analysis.The transformation efficiency 74.3% of 1-methoxyl group-2-propyl alcohol.Ketone yield 63.0%.。By product mainly is propionic aldehyde, acetone and methyl alcohol.
Example 3
Filling 5g 15%Ag in reactor
2O-19.5%NiO/r-Al
2O
3, other condition is identical with example 1.The transformation efficiency 73.3% of 1-methoxyl group-2-propyl alcohol, ketone yield 45.7%.
Example 4
Filling 5g 1.5%MgO-15%CuO-19.5%NiO/ silica gel in reactor, other condition is identical with example 1.The transformation efficiency 80% of 1-methoxyl group-2-propyl alcohol, ketone yield 67.5%.Be continuously pumped into 24 hours catalytic activitys with fresh feed pump and do not have bigger variation.Can onlinely regenerate behind the catalyst deactivation, promptly stop charging, continue blowing air after 3-4 hour, it is active that catalyzer can recover fully.
Example 5
Press example 2 described reactions, adopt different catalysts to carry out, it the results are shown in table 1.
As can be seen from Table 1, the catalytic activity of different catalysts main body has very big difference, and is best with the effect of cupric oxide.The charge capacity of catalyzer also has very big influence to the catalytic activity of 1-methoxyl group-2-propyl alcohol simultaneously.By a series of investigation, find that cupric oxide, nickel oxide have very strong concerted catalysis activity, nickel oxide shows the extremely strong catalytic activity that helps.Be with r-Al in the table 1
2O
3Investigated of the influence of catalyzer composition as carrier to catalytic activity.
Table 1 catalyzer is formed the influence to catalytic activity
No. catalyzer is formed (wt%) transformation efficiency (%) yield (%)
1 15％MoO
3 73.1 11.9
2 15％CuO 36.7 24.5
3 19.5％NiO 8.1 4.3
4 15％CuO-6.5％NiO 59.5 47.1
5 15％CuO-19.5％NiO 78.8 62.9
6 15％Ag
2O-19.5％NiO 73.3 45.7
7 15％CuO-19.5％Cr
2O
3?86.0 28.3
Reaction conditions: 300 ℃ of temperature of reaction, air speed 2.4ml/g.h, flow rate of carrier gas 1482ml/h.
Example 6
Press example 2 described reactions, adopt different catalysts to carry out, it the results are shown in table 2.As can be seen from Table 2, the used carrier of the present invention to transformation efficiency to influence difference little, have ubiquity.But the acidity of carrier itself has very big influence to the selectivity of reaction.1-methoxyl group-2-propyl alcohol and methoxy acetone all can carry out acidolysis on the acidic site of carrier, main by product is propionic aldehyde, methyl alcohol and acetone.Better with the effect of molecular sieve, aluminium sesquioxide and silica gel in used carrier, and the result of 4A molecular sieve is the poorest.The existence of metal such as lithium, potassium can weaken the acidity of carrier, thereby can suppress the sour decomposition reaction of 1-methoxyl group-2-propyl alcohol and methoxy acetone, and the methoxy acetone selectivity is improved.
Table 2 different carriers is to the influence of catalytic activity
No. carrier transformation efficiency (%) yield (%)
8 15％CuO-19.5NiO％/r-Al
2O
3 78.8 62.9
9 15％CuO-19.5NiO％/SiO
2 77.5 65.5
10 15%CuO-19.5NiO%/γ molecular sieve 74.3 63.0
11 15%CuO-19.5NiO%/molecular sieve 77.4 48.3
12 15%CuO-19.5NiO%/4A molecular sieve 65.4 27.0
13 15%CuO-19.5NiO%/acidity-Al
2O
3 *82.3 41.6
14 3%K
2O15%CuO-19.5NiO%/acidity-Al
2O
3 *70.0 64.1
Reaction conditions: 300 ℃ of temperature of reaction, air speed 2.4ml/g.h, flow rate of carrier gas 1482ml/h.
*Flow rate of carrier gas 850ml/h, air speed 2.2ml/g.h
Example 7
Pressing example 2 described reactions, is that example is investigated the influence of reaction conditions to catalytic activity with the 15%CuO-19.5%NiO/Y molecular sieve, and it the results are shown in Table 3.Temperature of reaction, air speed and flow rate of carrier gas obviously affect 1-methoxyl group-2-propyl alcohol oxidative dehydrogenation as shown in Table 3.Generally between 250-350 ℃, the air speed scope is 1.4-4.3ml/g.h to temperature of reaction, and flow rate of carrier gas can change between 500-2000ml/h.When temperature of reaction is 300 ℃, air speed is 2.4ml/g.h, and when flow rate of carrier gas was 1482ml/h, 1-methoxyl group-2-propyl alcohol can well be converted into product, and the yield of methoxy acetone is preferably 63%.
Table 3 reaction conditions is to the influence of catalytic activity
No. reaction conditions I reaction conditions II reaction conditions III transformation efficiency (%) yield (%)
15 250℃ 1482.5ml/h 2.4ml/g.h 59.1 25.1
16 300℃ 1482.5ml/h 2.4ml/g.h 74.3 63
17 350℃ 1482.5ml/h 2.4ml/g.h 89.3 49.9
18 300℃ 1482.5ml/h 1.5ml/g.h 80.3 47.8
19 300℃ 1482.5ml/h 2.4ml/g.h 74.3 63
20 300℃ 1482.5ml/h 4.3ml/g.h 71.1 53.5
21 300℃ 566.4ml/h 2.4ml/g.h 69.6 53.7
22 300℃ 806.3ml/h 2.4ml/g.h 72.2 53.8
23 300℃ 1482.5ml/h 2.4ml/g.h 74.3 63
24 300℃ 1831.8ml/h 2.4ml/g.h 67.1 50.4
Can be seen that by above-mentioned sample result the present invention has following outstanding effect: 1. preferably resolve the problem of oxidation of 1-methoxyl group-2-propyl alcohol, catalytic activity is far above the result of known technology; 2. preferably resolve the separation problem of product from system, the transformation efficiency of 1-methoxyl group-2-propyl alcohol is high more, helps the separation of methoxy acetone more; 3. it is cheap to have satisfied industrial production requirement 4. catalyzer raw materials basically, easily synthetic, directly uses oxidation state, does not need reduction activation; 5. have the life-span preferably, but in-situ regeneration behind the catalyst deactivation.
Claims (6)
1. a catalyzer that is used for the oxidative dehydrogenation of 1-methoxyl group-2-propyl alcohol is characterized in that being represented by formula M NP/Z, wherein:
M represents that the activity of such catalysts component is the oxide compound of Cu, Ag or Mo;
N represents that promotor is a kind of or two kinds in the oxide compound of Mg, Ni or Cr;
P represents that promotor is the oxide compound of Li, K or Ce;
Z represents that carrier is molecular sieve, Al
2O
3Or SiO
2
Active ingredient M content is the 5-20% of catalyst weight;
Promotor N content is the 0-20% of catalyst weight;
Promotor P content is the 0-10% of catalyst weight;
All the other are carrier Z.
2. catalyzer according to claim 1 is characterized in that M is the oxide compound of Cu, and N is the oxide compound of Ni, and the weight ratio of M: N is 0.5: 1-2.5: 1.
3. catalyzer according to claim 1 is characterized in that P is the oxide compound of K, and the content of P is the 0.5-5% of catalyst weight.
4. described Preparation of catalysts method of claim 1, be to adopt pickling process that active ingredient and cocatalyst component are supported on the carrier, it is characterized in that it being solution impregnating carrier Z with the soluble salt of the element that contains the element of active ingredient M and/or cocatalyst component N and P, then after drying, obtain catalyzer in 350-700 ℃ of following roasting; Described soluble salt is nitrate, vitriol or the muriate that contains the element of active ingredient M, cocatalyst component N and P.
5. catalyzer according to claim 4 is characterized in that at first dipping M and/or N component on carrier Z, floods the P component after drying again.
6. the oxidation of 1-methoxyl group-2-propyl alcohol prepares the reaction of methoxy acetone, it is characterized in that application rights requires 1 described catalyzer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011312920A CN1150153C (en) | 2001-09-05 | 2001-09-05 | Catalyst for preparing methoxy acetone and its prepn and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011312920A CN1150153C (en) | 2001-09-05 | 2001-09-05 | Catalyst for preparing methoxy acetone and its prepn and application |
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| CN1150153C true CN1150153C (en) | 2004-05-19 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0327514D0 (en) * | 2003-11-26 | 2003-12-31 | Davy Process Techn Ltd | Catalyst |
| CN104399474A (en) * | 2014-11-20 | 2015-03-11 | 西安近代化学研究所 | Catalyst for synthesizing methoxy acetone through alcohol dehydrogenization, preparation method and application of catalyst |
| CN105384616A (en) * | 2015-10-29 | 2016-03-09 | 山东联创节能新材料股份有限公司 | Synthetic method for methoxyacetone |
| CN107628933B (en) * | 2017-09-28 | 2020-08-14 | 中触媒新材料股份有限公司 | Continuous production process for synthesizing 1-methoxy-2-acetone by directly dehydrogenating 1-methoxy-2-propanol |
| CN107790128A (en) * | 2017-09-28 | 2018-03-13 | 中触媒新材料股份有限公司 | A kind of catalyst in the acetone synthetic reaction of 1 methoxyl group 2 and preparation method thereof |
| CN112844248B (en) * | 2020-12-28 | 2022-07-12 | 山东滨农科技有限公司 | Dehydrogenation interlocking control method for preparation of s-metolachlor raw pesticide |
| CN115106115B (en) * | 2021-03-19 | 2023-11-03 | 中国石油大学(华东) | Method for preparing acetone from alkane |
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