CN1232352C - Heteropoly compound catalyst, preparing method and application thereof - Google Patents
Heteropoly compound catalyst, preparing method and application thereof Download PDFInfo
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- CN1232352C CN1232352C CN 03139669 CN03139669A CN1232352C CN 1232352 C CN1232352 C CN 1232352C CN 03139669 CN03139669 CN 03139669 CN 03139669 A CN03139669 A CN 03139669A CN 1232352 C CN1232352 C CN 1232352C
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- heteropoly compound
- catalyst
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- acid
- phosphorus molybdenum
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Abstract
The present invention relates to heteropoly compound catalyst, a preparing method thereof and a method for preparing acrylic acid by using the catalyst for one-step selective oxidiation of propene. The heteropoly compound catalyst is composed of a phosphorus-molybdenum series heteropoly compound and carriers, wherein the general formula of the phosphorus-molybdenum series heteropoly compound is as follows: PMoaVbTecAsdM<1>eM<2>fOx. In the method for preparing acrylic acid by using the catalyst for one-step selective oxidiation of propene, a raw gas mixture comprising propene and oxygen or air or nitrogen carries out selective oxidation reaction under the action of the heteropoly compound catalyst. The present invention has the advantages of process simplification, investment saving and manufacturing cost reduction, and makes the replacement of two-step acrylic acid preparing methods possible.
Description
Technical field
The present invention relates to Heterocompound catalyst and preparation method thereof and be used for propylene (C
3 =) step selective oxidation production acrylic acid, propylene and oxygen or air, nitrogen material gas mixtures such as (having or dry-steam) carry out the selective oxidation reaction by the polycomponent Heterocompound catalyst specifically, one step generated vinylformic acid, had highly selective; The only a spot of acetate of by-product, propenal etc.
Background technology
Vinylformic acid (CH
2=CHCOOH) be important industrial raw material.Known acrylic acid derivative is more than thousand kinds, and what wherein have industrial production and application reaches tens of kinds, also has the trend that continues increase.Acrylate is the important source material of preparation polymkeric substance.The polymkeric substance of esters of acrylic acid has heat resistanceheat resistant, fast light and be difficult for oxygenolysis, can form soft and characteristics such as resilient diaphragm are widely used in numerous industrial sectors such as coating, material of construction, fabric and non-woven fabric, papermaking, leather, tackiness agent.Vinylformic acid also is one of important source material of water-soluble polymers, and polyacrylic acid and its esters are widely used as dispersion agent, thickening material, flocculation agent, tackiness agent, coating-forming agent by many industrial sectors and as High hydrophilous resin of the sanitary product or the usefulness of improving the soil etc.In recent years the liquid crystal type acrylate of external exploitation has excellent physics and chemistry and optical property, has broad application prospects in high-tech areas such as polymer science, life science, environmental science, information science and modern communication, household electrical appliance and precision instruments.
As far back as the sixties in last century, the propylene oxidation step is produced acrylic acid technology and once was used for industrial production, but because the vinylformic acid selectivity is not high, and replaced by two-step approach.So-called two-step approach.Be propenal with propylene oxidation earlier exactly, further be oxidized to vinylformic acid again.One segment base is polycomponent double oxide catalyzer [United States Patent (USP) 2904580 (1959)] in the Mo-Bi of SOHIO company exploitation; Two segment bases are developed in Distillers company, based on the polycomponent double oxide catalyzer [English Patent 903034 (1962)] of Mo-V.For many years, constantly improve through many companies (as companies such as Shell, Vgilor, BASF AG and Japanese catalyst, Japanese chemical drug, the people of Mitsubishi silk, Japan Cao Da), at present, propylene conversion is about 90% in one section reaction, and the propenal selectivity is about 78%; Two sections acrolein conversion rate are about 95%, and the vinylformic acid selectivity is 85-90%.Two steps added up to the about 60-70% of vinylformic acid total recovery.Two-step approach adopts two reactors in series, and flow process is longer, and equipment is huge.Investment and maintenance cost, product cost and energy consumption are all corresponding bigger.
Summary of the invention
The object of the present invention is to provide a kind of Heterocompound catalyst, be used for the propylene oxidation step and generate vinylformic acid, its selectivity is improved greatly, only a spot of acetate of by-product, propenal etc.Thereby simplified flow process, saved investment, reduced productive expense, strengthened competitiveness of product.Make two steps of replacement produce acrylic acid and become possibility.
The present invention also aims to provide the preparation method of described Heterocompound catalyst.
The present invention also aims to provide described Heterocompound catalyst to be used for the propylene oxidation step and generate acrylic acid.
Heterocompound catalyst of the present invention is that heteropoly compound and carrier are formed by the phosphorus molybdenum, and the phosphorus molybdenum is that the weight ratio of heteropoly compound and carrier is 1/2-2/1, is the best with 1/1.
The general formula that described phosphorus molybdenum is a heteropoly compound is: PMo
aV
bTe
cAs
dM
1 eM
2 fO
x
Wherein: M
1Be Cu, Ag, Ni and/or Fe, M
2Be Co, Mn, Cr and/or Ce, a=11-8, b=1-2, c=0-1, d=0.2-1.2, optimum value is 0.6-1.0, e=0.2-2.0, optimum value is 0.6-1.5, f=0.2-0.8, optimum value is 0.3-0.6, x is the numerical value of being determined by the valence state of element beyond the oxygen and atomicity;
The carrier of catalyzer can be SiO
2, Al
2O
3, TiO
2, or ZrO
2, with SiO
2Optimum.
The preparation method that phosphorus molybdenum of the present invention is a heteropoly compound comprises: with phosphoric acid, arsenic acid, molybdic oxide, Vanadium Pentoxide in FLAKES, tellurium dioxide or telluric acid and M
1, M
2Corresponding metal salt or oxide compound mix with deionized water, stir, and are heated to 60-90 ℃, and Heating temperature is best 70-80 ℃; 48-72 hour heat-up time, reflux, until the solid chemical compound dissolving, obtain being yellow-green soln, solution is filtered, concentrates, obtain Heterocompound catalyst with immersion process for preparing.
Phosphoric acid, arsenic acid, molybdic oxide, Vanadium Pentoxide in FLAKES tellurium dioxide or telluric acid, M
1, M
2The consumption of corresponding metal salt or oxide compound, deionized water can calculate according to the molecular formula of compound.
Heterocompound catalyst of the present invention is used for the propylene oxidation step, and to generate acrylic acid be that propylene and oxygen or air, nitrogen mixture carry out the selective oxidation reaction under the Heterocompound catalyst effect, temperature of reaction 350-380 ℃, a step generates vinylformic acid; Described unstripped gas consumption C
3H
6: O
2: N
2(H
2O)=5: 5-10: 20-15 (volume), air speed is 600-1200h
-1, with 690-960h
-1Be the best; Preheating temperature is 250-300 ℃.
Reaction can be carried out at flow reactor of fixed bed or in shell and tube reactor.
The purity of propylene is technical grade, promptly 〉=98%.As oxygen source can be oxygen or air.
Unstripped gas also can comprise water vapour, and its consumption is for replacing N
2The 0-50% volume, introduce water vapor and help to take away the oxidizing reaction liberated heat, the stopping reaction temperature prevents " temperature runaway ".
The present invention compared with prior art has following advantage:
(1) the present invention is used for the propylene one-step oxidation process with new catalyst and has vinylformic acid yield height, the characteristics that selectivity is good.Under optimum, the vinylformic acid yield is greater than 60% (selectivity about 80%), also recyclable utilizations such as by-product acetate.And remaining unreacted propylene (about 25%) is very easily separated, enters reactor again, recycles.
(2) the present invention compares with selective oxidation generation acrylic acid new catalyst with two step method, owing to saved a reactive system, has saved investment, has reduced productive expense and energy consumption.Thereby also reduced product cost, improved competitive power.
(3) produce acrylic acid equipment and product separation and purification techniques with two step method and go for the new method of oxidation step of the present invention fully.Thereby old factory is used instead new method do not have in principle difficulty, and acrylic acid throughput can improve greatly.
Embodiment
In the following embodiments, employing be miniature flow reactor of fixed bed, stainless steel, internal diameter 6mm, long 300mm, catalyst levels 2ml.
Embodiment 1
Preparation of Catalyst: take by weighing MoO
345 grams, V
2O
56.32 gram, Cu powder 1.43 grams are put into the 1000ml Erlenmeyer flask, add the 500ml deionized water, add H again
3PO
4(85%) 4.00 gram, H
3AsO
4(85%) 3.70 gram; In addition with H
2TeO
42H
2O 3.98 grams are dissolved in the 100ml deionized water, add in the Erlenmeyer flask in the lump after waiting to dissolve.Reflux condensing tube is installed, and Erlenmeyer flask is put into water-bath (2000ml beaker).Warming while stirring on magnetic stirrer is kept bath temperature 70-75 ℃, reacts 48 hours, until whole dissolvings.Add Co (NO then
3)
36H
2The O4.04 gram, restir is poured out solution in the furnace pot for a moment, concentrates in water-bath, obtains concentrated solution, and is standby.A certain amount of silica gel was toasted 1 hour under infrared lamp, then, pour a certain amount of concentrated catalyst solution into, continue under infrared lamp, to be baked to dried.Bottling, standby.
Catalyzer consists of: PMo
9V
2TeAs
0.6Cu
1.3Co
0.2Ox/SiO
2
Reaction conditions and reaction result such as table 1:
Table 1 (AL--propenal; Ace--acetone; HAc--acetate; AA--vinylformic acid)
| Reactor feed gas is formed air speed transformation efficiency yield/% selectivity temperature/℃ C 3 ＝∶O 2∶N 2 h -1 /％ AL Ace HAc AA CO CO 2 AA/％ |
| 360 5∶8∶10 690 69.2 1.4 0.6 13.8 51.4 1.3 0.7 74.3 370 5∶8∶10 690 69.2 1.8 0.5 14.6 50.3 1.3 0.7 72.7 370 5∶8∶10 690 74.0 1.0 0.5 11.7 57.2 2.5 1.1 77.1 380 5∶8∶10 690 79.5 0.9 0.5 10.2 64.7 3.2 81.3 380 5∶8∶10 690 79.4 0.9 0.6 6.5 68.1 3.3 86.0 380 5∶8∶10 690 81.9 1.2 1.0 11.1 64.6 3.5 0.5 79.9 390 5∶8∶10 690 69.0 1.5 0.5 8.4 53.2 3.2 2.2 76.9 |
Table 1 result demonstration, and under optimum (380 ℃, air speed 690h
-1), propylene conversion 80%, the vinylformic acid selectivity is up to more than 80%, and the vinylformic acid yield is more than 65%.
Embodiment 2:
Method for preparing catalyst such as embodiment 1.The change reaction conditions obtains the result as table 2:
Catalyzer consists of: PMo
9V
2TeAs
0.6Cu
1.3Co
0.2Ox/SiO
2
Table 2 (AL--propenal; Ace--acetone; HAc--acetate; AA--vinylformic acid)
| Temperature of reaction unstripped gas air speed transformation efficiency yield/% selectivity/℃ C 3 ＝∶O 2∶N 2 h -1 /％ AL Ace HAc AA CO CO 2 AA/％ |
| 360 5∶8∶15 840 59.7 2.1 0.6 12.6 42.0 1.9 0.5 70.4 380 5∶8∶15 840 67.7 1.1 0.5 8.8 53.0 3.2 1.1 78.3 380 5∶8∶15 840 70.1 0.9 0.4 9.2 56.2 2.8 0.6 80.2 380 5∶8∶15 840 71.3 0.9 0.4 9.3 57.0 3.1 0.6 79.9 390 5∶8∶15 840 71.1 1.0 0.5 7.9 56.0 3.5 1.5 78.8 390 5∶8∶15 840 69.0 1.0 0.5 7.9 55.0 3.2 1.4 79.7 400 5∶8∶15 840 68.9 1.5 0.6 7.1 51.9 6.5 1.3 75.3 |
Table 2 result shows, improves air speed, reaches 840h
-1, propylene conversion slightly reduces, and still reaches 70%, and the vinylformic acid selectivity keeps 80%, vinylformic acid yield about 56%.But because air speed improves, the throughput of catalyzer is constant substantially.
Embodiment 3:
Method for preparing catalyst such as preceding, but suitably adjust each amounts of components of catalyzer.
Catalyzer is composed as follows: PMo
8AsTeV
2Cu
1.0Co
0.4Ce
0.3Ox/SiO
2
Reaction conditions and reaction result such as table 3:
Table 3 (AL--propenal; Ace--acetone; HAc--acetate; AA--vinylformic acid)
| Temperature of reaction unstripped gas air speed transformation efficiency yield/% selectivity/℃ C 3 ＝∶O 2∶N 2 h -1 /％ AL Ace HAc AA CO CO 2 AA/％ |
| 380 5∶8∶11 720 72.5 5.1 1.0 7.0 54.1 4.8 0.5 74.6 390 5∶8∶11 720 71.3 2.3 0.7 9.3 53.3 5.0 0.7 74.8 380 5∶8∶15 840 68.4 2.5 0.5 9.9 47.1 5.4 6.4 68.9 390 5∶8∶15 840 73.4 2.4 0.6 11.5 53.1 5.4 0.4 72.3 400 5∶8∶15 840 74.1 8.7 0.8 4.9 51.6 7.5 0.6 69.6 380 5∶8∶19 960 72.4 4.2 0.8 10.2 52.1 4.5 0.6 72.0 |
Table 3 result shows, changes catalyzer and forms, and catalytic performance changes to some extent, propylene conversion 70%, and the vinylformic acid selectivity is more than 70%, and the vinylformic acid yield is more than 50%.
Claims (6)
1, a kind of Heterocompound catalyst is characterized in that by the phosphorus molybdenum being that heteropoly compound and carrier are formed, and the phosphorus molybdenum is that the weight ratio of heteropoly compound and carrier is 1/2-2/1, and the general formula that described phosphorus molybdenum is a heteropoly compound is: PMo
aV
bTe
cAs
dM
1 eM
2 fO
x
Wherein: M
1Be Cu, Ag, Ni and/or Fe,
M
2Be Co, Mn, Cr and/or Ce,
A is 11-8,
B is 1-2,
C is 0-1,
D is 0.2-1.2,
E is 0.2-2.0,
F is 0.2-0.8,
X is the numerical value of being determined by the valence state of element beyond the oxygen and atomicity;
The carrier of catalyzer is SiO
2, Al
2O
3, TiO
2, or ZrO
2
2, Heterocompound catalyst according to claim 1 is characterized in that the phosphorus molybdenum is that the weight ratio of heteropoly compound and carrier is 1/1, and described phosphorus molybdenum is that the d in the heteropoly compound general formula is 0.6-1.0, and e is 0.6-1.5, and f is 0.3-0.6, and carrier is SiO
2
3, the preparation method of the described Heterocompound catalyst of claim 1 is characterized in that described phosphorus molybdenum is that heteropoly compound prepares by following method: with phosphoric acid, arsenic acid, molybdic oxide, Vanadium Pentoxide in FLAKES tellurium dioxide or telluric acid and M
1, M
2Corresponding metal salt or oxide compound mix with deionized water, stir, and are heated to 60-90 ℃, reflux 48-72 hour heat-up time, until the solid chemical compound dissolving, obtain being yellow-green soln, and solution is filtered, concentrates.
4, the preparation method of Heterocompound catalyst according to claim 3 is characterized in that Heating temperature is 70-80 ℃.
5, the described Heterocompound catalyst of claim 1 is used for propylene oxidation step generation acrylic acid, the material gas mixture that it is characterized in that propylene and oxygen or air, nitrogen carries out the selective oxidation reaction under the Heterocompound catalyst effect, temperature of reaction 350-380 ℃, a step generates vinylformic acid; Described unstripped gas consumption C
3H
6: O
2: N
2=5: 5-10: 20-15 volume ratio, air speed are 600-1200h
-1, preheating temperature is 250-300 ℃.
6, Heterocompound catalyst according to claim 5 is used for propylene oxidation step generation acrylic acid, it is characterized in that unstripped gas also comprises water vapour, and its consumption is for replacing N
2The 0-50% volume, air speed is 690-960h
-1
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