CN1226095C - Solid phosphoric acid catalyst and its prepn process - Google Patents
Solid phosphoric acid catalyst and its prepn process Download PDFInfo
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- CN1226095C CN1226095C CN 02151168 CN02151168A CN1226095C CN 1226095 C CN1226095 C CN 1226095C CN 02151168 CN02151168 CN 02151168 CN 02151168 A CN02151168 A CN 02151168A CN 1226095 C CN1226095 C CN 1226095C
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- catalyst
- phosphoric acid
- solid phosphoric
- component
- acid catalyst
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Abstract
The present invention relates to a solid phosphoric acid catalyst and a preparation process thereof, which mainly solved the defects of no hydrolytic resistance of the catalyst and the poor crushing resisting strength of the catalyst in the prior. The solid phosphoric acid catalyst is represented as the following chemistry general formula of A1BaWb (P2O5)c (H2O)d calculated by molar ratio, wherein A is Si, B is selected from boron, antimony, bismuth and magnesium or a mixture of the elemments, W is tungsten, and a, b, c and d are mole numbers of the corresponding component when a component A is equal to 1. The preparation process of the catalytic comprises: firstly, preparing preheated polyphosphoric acid and a component B into polyphosphate; then, blending a mixture containing the component A and a component W; molding, drying, calcining and activating a formed material to obtain the finished catalyst, wherein the component W is in a heteropolyacid form of the tungsten to be attracted. The catalyst has the characteristics of good hydrolytic resistance and high crushing resisting strength. Simultaneously, the catalyst still keeps high catalysis activity. The solid phosphoric acid catalyst can be used for industrial production.
Description
Technical field
The present invention relates to a kind of solid phosphoric acid catalyst and preparation method thereof.
Background technology
Solid phosphoric acid catalyst (SPAC) is one of widely used catalyst in the petro chemical industry, be applied to reactions such as the oligomerisation of low-carbon alkene, superimposed, hydrocarbonylation, solid phosphoric acid catalyst is mainly by phosphoric acid or polyphosphoric acids with contain silicon carrier and make, the preparation method comprises infusion process and blending method, early stage research people adopt the immersion process for preparing solid phosphoric acid catalyst more, but because the manufacturing cycle is long, the catalyst activity that makes is not high, is not widely used; Blending method is that phosphoric acid or polyphosphoric acids and diatomite are carried out blending reaction, introduces the 3rd component, makes through extrusion, drying, roasting, activation.This method is even owing to having mixing of materials, and active high characteristics become the main direction that these those skilled in the art study.The great advantage of solid phosphoric acid catalyst is that phosphoric acid and diatomite generate phosphoric acid silicon under suitable temperature action, phosphoric acid is adsorbed more securely with diatomite and/or combine, have acid and be difficult for running off in commercial Application, the catalytic activity height does not cause characteristics such as corrosion to equipment; And that the disadvantage of solid phosphoric acid catalyst is a mechanical strength is low, during reaction phosphoric acid silicon under the steam effect, expand easily, deliquescing, argillization, cause the beds pressure drop to increase, make the dismounting of device catalyst frequent, bring very big difficulty to normal production, catalyst life shortens.Therefore, people also very pay close attention to the research work that improves catalyst strength and water resistance, with the advantage of better performance solid phosphoric acid catalyst when making great efforts to improve catalyst activity.
Patent CN1049373A discloses a kind of phosphoric acid/active carbon catalyst and coincidence process, and catalyst adopts immersion process for preparing, and the processed active carbon carrier is immersed in the industrial phosphoric acid, added hot reflux 2～8 hours in 100～110 ℃ of dippings, after filtration, drying, activation makes the catalyst finished product.Evaluating catalyst is 130～230 ℃ of reaction temperatures, raw material air speed 2.5～5.0hr
-1, under reaction pressure 2.0～6.0MPa condition, mixed olefins or C
4Alkene contacts with catalyst and carries out building-up reactions and prepare high-knock rating gasoline, and the maximum conversion of alkene is 72.44%, and the axial crushing strength of the catalyst that makes is relatively poor, have only 170 newton/centimetre
2, make catalyst stability relatively poor.
Chinese patent 92103504.7 (CN1032121C) discloses a kind of solid phosphoric acid catalyst that is used for olefin(e) oligomerization, and this catalyst is made up of following general formula: AB
aC
b(P
2O
5)
c(H
2O)
dA=Si in the formula; B=Cu, Fe, Ni; C=B, Sb, Bi; This catalyst is mainly used in propylene oligomerization and produces nonene and laurylene, 200 ℃ of reaction temperatures, and reaction raw materials air speed 2.0hr
-1, under the reaction pressure 4.0MPa condition, the propylene average conversion is 78.2%, the axial crushing strength of catalyst be 480 newton/centimetre
2
Chinese patent 00116525.9 has been introduced a kind of solid phosphoric acid catalyst that is used for olefin(e) oligomerization or hydrocarbonylation, and its composition is represented by following chemical general formula with molar ratio computing: SiA
aB
b(P
2O
5)
c(H
2O)
dA is selected from least a in boron, aluminium or the indium in the formula, B is selected from least a in titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or the tungsten, the a value is 0.1～1.5, the b value is 0.005～0.2, the c value is 1.0～2.0, and the d value is 0.6～1.1, and a, b, c, d equal the atomicity of 1 o'clock respective element for the Si atom.This catalyst is used for propylene oligomerization and produces nonene and laurylene, has good activity and selectivity, crush strength be 1000 newton/centimetre
2, but do not relate to the water resistance of catalyst.
Compare with solid phosphoric acid catalyst in the past, this activity of such catalysts, crush strength have had than much progress, but this patent does not relate to the water resistance of catalyst, and the intensity of catalyst does not reach perfect condition yet.With regard to industrial production, what people pursued is longer catalyst life, can save production cost, and extends manufacture cycle, and obtains higher product yield simultaneously, could increase the production capacity of device like this, increases economic efficiency.Therefore, a kind of to have high strength, water resistance solid phosphoric acid catalyst good, that have a high catalytic activity simultaneously be people's long-term aim in research.
Summary of the invention
One of the object of the invention is not relate to the catalyst water resistance in the conventional art in order to overcome, the defective that the crush strength of catalyst is desirable not enough, a kind of new solid phosphoric acid catalyst is provided, it is good that this catalyst has a water resistance, the characteristics that crush strength is high, catalyst still keeps advantages of high catalytic activity simultaneously.
Two of the object of the invention provides the preparation method of the solid phosphoric acid catalyst that one of a kind of and purpose adapt.
One of the object of the invention is achieved through the following technical solutions: a kind of solid phosphoric acid catalyst, and its composition is represented by following chemical general formula with molar ratio computing:
A
1B
aW
b(P
2O
5)
c·(H
2O)
d
A is Si in the formula, and B is selected from boron, antimony, bismuth, magnesium or their mixture, and W is a tungsten; The a value is 0.2～0.6, and the b value is 0.01～0.2, and the c value is 1.1～1.8, and the d value is 0.6～1.3, and a, b, c, d equal the molal quantity of 1 o'clock corresponding component for the A component.
A value preferable range is 0.3～0.5 in the technique scheme, and b value preferable range is 0.05～0.14, and c value preferable range is 1.2～1.6, and d value preferable range is 0.8～1.1.
Two of the object of the invention is achieved through the following technical solutions: a kind of preparation method of solid phosphoric acid catalyst, earlier polyphosphoric acids and B component stirring reaction under 120～200 ℃ of conditions of preheating are made polyphosphate, then with the mixture blend of the heteropoly acid that contains A component and tungsten, form the plaster material of viscosity, material is through behind the extruded moulding, and drying was in 350～700 ℃ of roastings 1～10 hour, adopt the gaseous mixture activation of air and water vapour again, obtain the catalyst finished product.
The used raw material of catalyst each component is as follows among the preparation method: the A component induces one with the diatomite form, the B component is introduced with the form of corresponding oxide, hydroxide or its decomposable salt, the heteropoly acid of tungsten can be silico-tungstic acid, phosphotungstic acid or its mixture, and the heteropoly acid of tungsten can be with pressed powder or aqueous solution form and A component (diatomite) blend formation mixture.
In the method for preparing catalyst, the polyphosphoric acids preheat temperature is 80～120 ℃, and polyphosphoric acids concentration is with P
2O
5Weight counts 70～85%, and the mol ratio of air and water vapour is 0.5～1.5: 1,200～300 ℃ of activation temperatures, soak time 2～6 hours.
The activity of such catalysts evaluation is carried out in fixed bed reactors, and reactor is a stainless steel tubular type reactor, 32 * 1000 millimeters of size Φ, 100 milliliters of interior loading catalysts.Adopt alkene (carbon three, C 4 olefin) as reaction raw materials, alkane (carbon three, butane) is made diluent, raw material olefin concentration 40～90% (quality), and all the other are alkane.160～220 ℃ of reaction temperatures, reaction pressure 3.0～6.0MPa, liquid volume air speed 1～4 hour
-1Under the process conditions, raw material olefin is contacted with catalyst of the present invention olefin oligomerization takes place.Reacted material comprises liquid product and gaseous stream, and by gas-liquid separator, liquid product enters liquid trap, and timing sampling analytical reactions product hydrocarbon composition, gaseous stream are that unreacted tail gas regularly enters online gas-chromatography and analyzes.
Analysis in the above-mentioned course of reaction and computational methods, be to feed intake stopping reaction after 12 hours, raw material and tail gas sample are answered in negate, analyze alkene, alkane quality percentage composition in raw material and the tail gas according to GB/T3392-91 (the mensuration gas chromatography of hydrocarbon impurities in propylene), calculate olefin conversion; The hydrocarbon composition of sampling analysis liquid product calculates selectivity of product.Wherein olefin conversion, selectivity of product are defined as follows:
Water resistance is the important criterion that embodies solid phosphoric acid catalyst stability, and the catalyst water resistance embodies with the soak loss rate of catalyst in water, the Strength Changes that places air to place front and back respectively among the present invention.
The soak test operation of catalyst sample is as follows: get a certain amount of catalyst sample, weigh, be recorded as W
1, in water, soaked 2～4 hours, filter out catalyst, 110 ℃ are dried to constant weight, weigh once more, are recorded as W
2, be calculated as follows catalyst soak loss rate: (W
1-W
2)/W
1* 100%.Catalyst soak loss rate is more little, and the water resistance of catalyst is good more, and catalyst soak loss rate of the present invention is less than 3.5%.
The catalyst crush strength is measured by the specification requirement of standard GB/T3635 (chemical fertilizer catalyst, molecular sieve, absorbent particles crush strength assay method) regulation, tester is a DL-II granule strength analyzer, the catalyst crushing strength of measuring is the broken power of axial compression resistance that unit are can be born, unit be newton/centimetre
2
Solid phosphoric acid catalyst provided by the invention is applicable to C
3Or/and C
4Olefin(e) oligomerization or building-up reactions prepare C
6～C
16Alkene is specially adapted to oligomerization of propene and produces nonene and laurylene, the superimposed production high-knock rating gasoline of C 4 olefin, and butene dimerization is produced technologies such as octene, all can obtain gratifying effect.
The present invention by add oxide, hydroxide or the salt that is selected from B, Sb, Bi or Mg element in P, Si system, makes catalyst have higher activity based on solid phosphoric acid; In P, Si system, introduce the heteropoly acid component of W simultaneously, improved the water resistance of catalyst especially effectively, and catalyst activity is not had a negative impact, make whole catalyst still keep high reaction activity and high.
The C of factory
3Or/and C
4General water content is in 500～3000ppm scope in the olefin feedstock, and general solid phosphoric acid catalyst is used for commercial plant when carrying out the long-term operation of oligomerization of propene or building-up reactions, often need carry out preliminary treatment to raw material, removes or reduces raw material institute water content.Catalyst of the present invention acts synergistically between each component owing to introduce the heteropoly acid component of tungsten, makes catalyst have water resistance preferably, compares with general solid phosphoric acid catalyst, to raw material C
3Or/and C
4Water content requires loosely in the alkene, and raw material needn't can directly use through dehydration preliminary treatment such as drying towers, has reduced production process, simplifies the operation course, and has prolonged catalyst service life, has obtained better effects.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
The preparation catalyst A:
Restrain concentration 83% (with P with 700
2O
5The weight meter) polyphosphoric acids places 2000 ml beakers, is heated to 100 ℃, under electronic stirring, adds 70 gram boric acid, reacts 30 minutes, makes polyphosphate; Simultaneously with 190 dry diatomite of gram and a certain amount of phosphotungstic acid H
7P (W
2O
7)
6XH
2O (x is generally between 9～17) places kneading machine, mix, add the polyphosphate that above-mentioned reaction is made, kneaded in kneading machine 5 minutes, blend is even, obtain a kind of plaster material of viscosity, this material extrusion is become 4 * 6～8 millimeters cylindrical particle, in 150 ℃ of dryings 2 hours, in 500 ℃ of constant temperature calcinings 5 hours, naturally cool to room temperature, obtain catalyst precarsor; Pack into then in the stainless steel tubular type activation tower of 50 * 1000 millimeters of Φ, bubbling air and water vapour activate, air: water vapour mol ratio 1.2: 1,200 ℃ of activation temperatures, soak time 3 hours.The solid phosphoric acid catalyst A that makes consists of:
Si
1B
0.42W
0.07(P
2O
5)
1.55·(H
2O)
0.8
According to aforesaid evaluating catalyst method, catalyst A is used for propylene oligomerization, the evaluation process conditions are: 200 ℃ of reaction temperatures, pressure 4.0MPa, liquid volume air speed 2.0 hours
-1, raw material propylene concentration 47% (quality), all the other are propane.Evaluating catalyst result: propylene conversion 82.5%, oligomerization of propene thing (nonene and laurylene) selectivity 85.6%.
[embodiment 2]
The preparation catalyst B:
According to the preparation method of embodiment 1, difference: replace 70 gram boric acid with 47 gram boron oxides, change the phosphotungstic acid consumption, a certain amount of phosphotungstic acid is made into 20% (weight) aqueous solution, be added to and be equipped with in the diatomaceous kneading machine, mix, the solid phosphoric acid catalyst B that makes consists of:
Si
1B
0.5W
0.15(P
2O
5)
1.55·(H
2O)
0.8
According to aforesaid evaluating catalyst method, catalyst B is used for the butene-2 oligomerisation reaction, the evaluation process conditions are: 180 ℃ of reaction temperatures, pressure 5.0MPa, liquid volume air speed 2.0 hours
-1, raw material butene-2 concentration 82.8% (quality).Evaluating catalyst result: butene-2 average conversion 84.0%, octene selectivity 88.5%.
[embodiment 3]
Preparation catalyst C:
According to the preparation method of embodiment 1, difference: replace boric acid with magnesia, with silico-tungstic acid (H
4SiW
12O
407H
2O) replace phosphotungstic acid, the solid phosphoric acid catalyst C that makes consists of:
Si
1Mg
0.2W
0.10(P
2O
5)
1.55·(H
2O)
0.8
According to the evaluation method evaluate catalysts of embodiment 1, the evaluating catalyst result is: propylene average conversion 80.8%, oligomerization of propene thing selectivity 83.4%.。
[embodiment 4]
Preparation catalyst D:
According to the preparation method of embodiment 1, difference: replace boric acid with antimony oxide, with silico-tungstic acid (H
4SiW
12O
407H
2O) replace phosphotungstic acid, the solid phosphoric acid catalyst D that makes consists of:
Si
1Sb
0.3W
0.12(P
2O
5)
1.55·(H
2O)
0.8
According to the evaluation method evaluate catalysts of embodiment 1, the evaluating catalyst result is: propylene average conversion 81.3%, oligomerization of propene thing selectivity 80.8%.
[comparative example 1]
According to the preparation method of embodiment 1, be 83% (with P with concentration
2O
5The weight meter) polyphosphoric acids 700 grams with 70 gram acid reactions, do not add the W component, knead in kneading machine evenly with the dry diatomite of 190 grams then.The catalyst that makes consists of:
Si
1B
0.42(P
2O
5)
1.55·(H
2O)
0.8
Catalyst materialization test result: crush strength 570 newton/centimetre
2
Use the evaluation method identical with embodiment 1, the evaluating catalyst result is: propylene conversion 79%, oligomer selectivity 79%.
[embodiment 5]
The experiment of catalyst water resistance
1. catalyst soak loss rate
Get the catalyst A sample 20 gram (W of embodiment 1 preparation with quartering
1), placing beaker, 200 milliliters of adding distil waters soaked 2 hours, filtered out catalyst, drained surperficial moisture content, were dried to constant weight in 110 ℃ then, weighed after the cooling, and weight is 19.3 gram (W
2), calculate catalyst soak loss rate, get the mean value of measuring for three times, the results are shown in table 1.
Measure the soak loss rate of catalyst B, C, D and comparative example 1 catalyst as stated above respectively, the results are shown in table 1.
2. catalyst crush strength
Get each 20 of the catalyst samples of embodiment 1～4 and comparative example 1 preparation with quartering, press the GB/T3635 method is measured catalyst with DL-II granule strength analyzer crush strength, the crush strength of catalyst calculates with the arithmetic mean of instantaneous value of 20 measurement results, the results are shown in Table 1.
Get each 20 of the catalyst samples of embodiment 1～4 and comparative example 1 preparation in addition with quartering, place air (humidity 50%) to place 4 hours, press the GB/T3635 method is measured catalyst with DL-II granule strength analyzer crush strength then, the crush strength of catalyst calculates with the arithmetic mean of instantaneous value of 20 measurement results, the results are shown in Table 1.
The contrast of table 1 catalyst water resistance
| Catalyst | Soak loss rate % | Intensity (newton/centimetre 2) | |
| Before placing in the air | After placing in the air | ||
| A | 3.5 | 1200 | 1100 |
| B | 2.0 | 1410 | 1340 |
| C | 3.1 | 1250 | 1150 |
| D | 2.8 | 1300 | 1220 |
| Comparative example | 6.4 | 600 | 350 |
Claims (8)
1, a kind of solid phosphoric acid catalyst, its composition is represented by following chemical general formula with molar ratio computing:
A
1B
aW
b(P
2O
5)
c·(H
2O)
d
A is Si in the formula, and B is selected from boron, antimony, bismuth, magnesium or their mixture, and W is a tungsten; The a value is 0.2～0.6, and the b value is 0.01～0.2, and the c value is 1.1～1.8, and the d value is 0.6～1.3, and a, b, c, d equal the molal quantity of 1 o'clock corresponding component for the A component.
2, solid phosphoric acid catalyst according to claim 1 is characterized in that a value is 0.3～0.5, and the b value is 0.05～0.14, and the c value is 1.2～1.6, and the d value is 0.8～1.1.
3, the preparation method of a kind of claim 1 or 2 described solid phosphoric acid catalysts, earlier polyphosphoric acids and B component stirring reaction under 120～200 ℃ of conditions of preheating are made polyphosphate, then with the mixture blend of the heteropoly acid that contains A component and tungsten, form the plaster material of viscosity, material is through behind the extruded moulding, and drying was in 350～700 ℃ of roastings 1～10 hour, adopt the gaseous mixture activation of air and water vapour again, obtain the catalyst finished product.
4,, it is characterized in that the A component induces one with the diatomite form according to the preparation method of the described solid phosphoric acid catalyst of claim 3.
5,, it is characterized in that of the form introducing of B component with corresponding oxide, hydroxide or its decomposable salt according to the preparation method of the described solid phosphoric acid catalyst of claim 3.
6, according to the preparation method of the described solid phosphoric acid catalyst of claim 3, the heteropoly acid that it is characterized in that tungsten is silico-tungstic acid, phosphotungstic acid or its mixture.
7, according to the preparation method of the described solid phosphoric acid catalyst of claim 3, it is characterized in that the polyphosphoric acids preheat temperature is 80～120 ℃, polyphosphoric acids concentration is with P
2O
5Weight counts 70～85%.
8, according to the preparation method of the described solid phosphoric acid catalyst of claim 3, the mol ratio that it is characterized in that air and water vapour is 0.5～1.5: 1,200～300 ℃ of activation temperatures, soak time 2～6 hours.
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|---|---|---|---|
| CN 02151168 CN1226095C (en) | 2002-12-11 | 2002-12-11 | Solid phosphoric acid catalyst and its prepn process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02151168 CN1226095C (en) | 2002-12-11 | 2002-12-11 | Solid phosphoric acid catalyst and its prepn process |
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|---|---|
| CN1506157A CN1506157A (en) | 2004-06-23 |
| CN1226095C true CN1226095C (en) | 2005-11-09 |
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| CN109395764B (en) * | 2018-12-18 | 2021-09-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of phosphorus-doped carbon nitride, product and application thereof |
| CN109731591B (en) * | 2019-01-17 | 2022-10-18 | 淮北师范大学 | Preparation method and application of bismuth phosphate with performance of removing VOC and EEDs simultaneously |
| CN109647462A (en) * | 2019-01-17 | 2019-04-19 | 淮北师范大学 | A kind of preparation method and application of Bi base catalyst |
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