CN1208130C - Prepn of solid phosphoric acid catalyst for oligomerization of low-carbon olefine - Google Patents
Prepn of solid phosphoric acid catalyst for oligomerization of low-carbon olefine Download PDFInfo
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- CN1208130C CN1208130C CNB021511691A CN02151169A CN1208130C CN 1208130 C CN1208130 C CN 1208130C CN B021511691 A CNB021511691 A CN B021511691A CN 02151169 A CN02151169 A CN 02151169A CN 1208130 C CN1208130 C CN 1208130C
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Abstract
The present invention relates to a preparation method of a solid phosphoric acid catalyst for the oligomerization of low carbon olefine. The defects of no hydrolytic resistance of the catalyst and the poor crushing resistant strength of the catalyst in the prior art are mainly overcome. In the preparation of the solid phosphoric acid catalyst of the present invention, polyphosphoric acid and a component containing B, Sb, Bi or Mg react to generate polyphosphate, and then, the polyphosphate and a silicon carrier are calcined at the first time after mixed; a heteropoly acid component is introduced in materials after calcined, and the materials are squeezed, formed, calcined again at high temperature and activated to prepare the finished catalyst. The catalyst prepared by the method of the present invention has the characteristics of good hydrolytic resistance and high crushing resistant strength. Simultaneously, the catalyst still maintains high catalytic activity. The present invention can be used for industrial production.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the solid phosphoric acid catalyst of low-carbon alkene oligomerisation.
Background technology
Solid phosphoric acid catalyst (SPAC) is one of widely used catalyzer in the petrochemical 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 acid with contain silicon carrier and make, the preparation method comprises pickling 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 acid 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 industrial 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 physical 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 catalyzer 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 catalyzer adopts immersion process for preparing, and the processed active carbon carrier is immersed in the industrial phosphoric acid, flooded reflux 2～8 hours in 100～110 ℃, after filtration, drying, activation makes the catalyzer finished product.Evaluating catalyst is 130～230 ℃ of temperature of reaction, raw material air speed 2.5～5.0hr
-1, under reaction pressure 2.0～6.0MPa condition, mixed olefins or C
4Alkene contacts with catalyzer and carries out building-up reactions and prepare stop bracket gasoline, and the peak rate of conversion of alkene is 72.44%, and the axial crushing strength of the catalyzer 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 oligomerization, and this catalyzer 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 catalyzer is mainly used in propylene oligomerization and produces nonene and laurylene, 200 ℃ of temperature of reaction, 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 catalyzer be 480 newton/centimetre
2
Chinese patent 00116525.9 has been introduced a kind of solid phosphoric acid catalyst that is used for olefin 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, aluminium 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 catalyzer 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 catalyzer.
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 catalyzer, and the intensity of catalyzer 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 throughput 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
Technical problem to be solved by this invention is to overcome not relate to the catalyzer water resistance in the conventional art, the crush strength of catalyzer is the ideal defective not enough, a kind of preparation method who is used for the solid phosphoric acid catalyst of low-carbon alkene oligomerisation is provided, it is good that the catalyzer that this method provides has a water resistance, the characteristics that crush strength is high, catalyzer still keeps advantages of high catalytic activity simultaneously.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: be used for the preparation method of the solid phosphoric acid catalyst of low-carbon alkene oligomerisation, wherein the catalyzer composition is represented by following chemical general formula with molar ratio computing: Si1A
aW
b(P
2O
5)
c(H
2O)
d, A is selected from boron, antimony, bismuth, magnesium or their mixture in the formula, 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, a, b, the mole number of corresponding component when c, d are Si=1, and Preparation of Catalyst may further comprise the steps successively:
A) polyphosphoric acid and A component are made polyphosphate at 120～200 ℃ of following stirring reactions, make its consumption satisfy the mole proportioning of above-mentioned general formula, keep this temperature of reaction with polyphosphate with contain the silicon carrier blend, obtain viscosity bulk material, dry then, in 300～400 ℃ of roastings 1～5 hour;
B) in the material after above-mentioned roasting, add the heteropolyacid aqueous solution of tungsten, blend is even, extruded moulding, and drying in 350～700 ℃ of roastings 1～4 hour, obtains catalyst precursor;
C) gas mixture with air and water vapor activates, 200～300 ℃ of activation temperatures, and soak time 2～6 hours, the mol ratio of air and water vapor is 0.5～1.5: 1, obtains the catalyzer finished product.
In the technique scheme, the used raw material of catalyzer each component is as follows: polyphosphoric acid concentration is with P
2O
5Weight counts 70～85%, and containing silicon carrier is diatomite or silicon-dioxide, and the A component is introduced with the form of corresponding oxide compound, oxyhydroxide or its decomposable salt, and the heteropolyacid of tungsten is selected from silicotungstic acid, phospho-wolframic acid or their mixture.In Preparation of Catalyst, the moulding of material for the benefit of and extruding smoothly can add an amount of extrusion aid such as talcum powder or sesbania powder during extrusion, and the extrusion aid add-on is 1～5% of a silicon carrier weight.
The material that obtains after the roasting of above-mentioned a step for block, certain fragility arranged, with the heteropolyacid aqueous solution of tungsten before, material can be crushed to particle diameter less than 1 millimeter, so that material obtains thorough mixing, the concentration of the heteropolyacid aqueous solution that uses is not particularly limited, and its weight concentration is generally 10%～and saturated.
In the technique scheme, the mol ratio preferable range of catalyzer each component: a value is 0.3～0.6, 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.
Activity rating of catalyst carries out in fixed-bed reactor, and reactor is a stainless steel tubular type reactor, 32 * 1000 millimeters of size Φ, 100 milliliters of interior loading catalysts.Adopt low-carbon alkene (carbon three and/or C 4 olefin) as reaction raw materials, alkane (carbon three and/or butane) is made thinner, raw material olefin concentration 40～90% (quality), and all the other are alkane.160～220 ℃ of temperature of reaction, reaction pressure 3.0～6.0MPa, liquid volume air speed 1～4 hour
-1Under the processing condition, raw material olefin is contacted with catalyzer 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 time sampling analytical reaction product hydrocarbon composition, gaseous stream are that unreacted tail gas regularly enters online gas-chromatography and analyzes.
Analysis in the above-mentioned reaction process and method of calculation, 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 vapor-phase 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 water resistance of the inventive method catalyzer embodies with the Strength Changes that soak loss rate, the humidity ability-catalyzer of catalyzer in water places air to place front and back respectively.
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 catalyzer, 110 ℃ are dried to constant weight, weigh once more, are recorded as W
2, be calculated as follows catalyzer soak loss rate: (W
1-W
2)/W
1* 100%.Catalyzer soak loss rate is more little, and the water resistance of catalyzer is good more, and the catalyzer soak loss rate of the inventive method preparation is less than 2.8%.
The catalyzer crush strength is measured by the technical requirements of standard GB/T3635 (chemical fertilizer catalyst, molecular sieve, absorbent particles crush strength measuring method) regulation, testing tool is a DL-II granule strength determinator, the catalyzer crushing strength of measuring is the broken power of axial compression resistance that unit surface can be born, unit be newton/centimetre
2
Solid phosphoric acid catalyst provided by the invention is applicable to C
3Or/and C
4Olefin 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 stop bracket gasoline of C 4 olefin, and butene dimerization is produced technologies such as octene, all can obtain gratifying effect.
The preparation method of solid phosphoric acid catalyst of the present invention, make polyphosphoric acid earlier and contain B, Sb, the component reaction of Bi or Mg generates polyphosphate, carry out the roasting first time then with after the silicon carrier blend, the heteropolyacid aqueous solution blend that adds tungsten in the material after roasting, behind extruded moulding, carry out the high-temperature roasting second time, by the synergy between each component and twice high-temperature calcination process, special water resistance and the crush strength that has improved catalyzer effectively, and catalyst activity is not had a negative impact, make whole catalyzer still keep high reaction activity and high.
The common C of factory
3Or/and C
4Water content is in 500～3000ppm scope in the olefin feedstock, when solid phosphoric acid catalyst is used for full scale plant and carries out the long-term operation of oligomerization of propene or building-up reactions in the past, often need carry out pre-treatment to raw material, removes or reduces raw material institute water content.The preparation method of solid phosphoric acid catalyst provided by the invention, introduce the heteropolyacid component of tungsten, and adopt the technical scheme of twice high-temperature roasting, obtained result beyond expectation, make the catalyzer of preparation have water resistance and crush strength preferably, compare with solid phosphoric acid catalyst in the past, to raw material C
3Or/and C
4Water-content requires loosely in the alkene, and raw material needn't can directly use through dehydration pre-treatment such as drying towers, has reduced production process, simplifies the operation course, and has prolonged catalyzer work-ing life, has obtained better effects.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
The preparation catalyst A:
Restrain concentration 83% (with P with 700
2O
5The weight meter) polyphosphoric acid places 2000 ml beakers, be heated to 100 ℃, under electronic stirring, add 100 gram boric acid, reacted 30 minutes, and made polyphosphate, polyphosphate is placed kneading machine, add the dry diatomite of 190 grams, kneaded 5 minutes, and obtained viscosity bulk material, then in 170 ℃ of dryings 1 hour, in 300 ℃ of constant temperature calcinings 2 hours, obtain the material after the roasting for the first time, this material is crushed to particle diameter less than 1 millimeter, join in the kneading machine, add 4 gram talcum powder then, the phospho-wolframic acid H of a certain amount of weight concentration 20%
7P (W
2O
7)
6XH
2O (x is generally 9～17) aqueous solution is kneaded, and blend is even, extrusion becomes 4 * 6～8 millimeters cylindrical particle, in 150 ℃ of dryings 2 hours,, naturally cool to room temperature in 550 ℃ of constant temperature calcinings 2 hours, obtain catalyst precursor, at last catalyzer is packed in the stainless steel tubular type activation tower of 50 * 1000 millimeters of Φ, bubbling air and water vapor activate, air: water vapor 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
0.6W
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 processing condition are: 200 ℃ of temperature of reaction, 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 82.8%, oligomerization of propene thing (nonene and laurylene) selectivity 84.0%.
[embodiment 2]
The preparation catalyst B:
According to the preparation method of embodiment 1, difference: replace 100 gram boric acid with 47 gram boron oxides, change the phospho-wolframic acid consumption, maturing temperature is 350 ℃ for the first time, and 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 processing condition are: 180 ℃ of temperature of reaction, 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 85.0%, octene selectivity 89.2%.
[embodiment 3]
Preparation catalyzer C:
According to the preparation method of embodiment 1, difference: replace boric acid with magnesium oxide, with silicotungstic acid (H
4SiW
12O
407H
2O) replace phospho-wolframic acid, do not add talcum powder, the solid phosphoric acid catalyst C that makes consists of:
Si
1Mg
0.4W
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 81.6%, oligomerization of propene thing selectivity 82.4%.
[embodiment 4]
Preparation catalyzer D:
According to the preparation method of embodiment 1, difference: replace boric acid with weisspiessglanz, with silicotungstic acid (H
4SiW
12O
407H
2O) replace phospho-wolframic 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 81.7%, oligomerization of propene thing selectivity 82.5%.
[comparative example 1]
The method of introducing according to patent 92103504.7 embodiment 1 prepares solid phosphoric acid catalyst, and the catalyzer that makes consists of: Si
1Cu
0.247B
0.6(P
2O
5)
1.45(H
2O)
0.8
Use the method identical with the embodiment of the invention 1 that catalyzer is estimated, the evaluating catalyst result is: propylene conversion 78%, oligopolymer selectivity 81%.
[embodiment 5]
The experiment of catalyzer water resistance
1. catalyzer 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 catalyzer, drained surperficial moisture content, were dried to constant weight in 110 ℃ then, weighed after the cooling, and weight is 19.5 gram (W
2), calculate catalyzer 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 catalyzer as stated above respectively, the results are shown in table 1.
2. catalyzer 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 catalyzer with DL-II granule strength determinator crush strength, the crush strength of catalyzer calculates with the arithmetical av 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 catalyzer with DL-II granule strength determinator crush strength then, the crush strength of catalyzer calculates with the arithmetical av of 20 measurement results, the results are shown in Table 1.
Table 1 catalyzer water resistance measurement result
| Catalyzer | Soak loss rate % | Intensity (newton/centimetre 2) | |
| Before placing in the air | After placing in the air | ||
| A | 2.5 | 1250 | 1150 |
| B | 2.0 | 1450 | 1380 |
| C | 2.8 | 1350 | 1250 |
| D | 2.5 | 1380 | 1290 |
| Comparative example | 5.8 | 540 | 350 |
Claims (7)
1, the preparation method who is used for the solid phosphoric acid catalyst of low-carbon alkene oligomerisation, wherein the catalyzer composition is represented by following chemical general formula with molar ratio computing: Si
1A
aW
b(P
2O
5)
c(H
2O)
d, A is selected from boron, antimony, bismuth, magnesium or their mixture in the formula, 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, a, b, the mole number of corresponding component when c, d are Si=1, and Preparation of Catalyst may further comprise the steps successively:
A) polyphosphoric acid and A component are made polyphosphate at 120～200 ℃ of following stirring reactions, make its consumption satisfy the mole proportioning of above-mentioned general formula, keep this temperature of reaction with polyphosphate with contain the silicon carrier blend, obtain viscosity bulk material, dry then, in 300～400 ℃ of roastings 1～5 hour;
B) in the material after above-mentioned roasting, add the heteropolyacid aqueous solution of tungsten, blend is even, extruded moulding, and drying in 350～700 ℃ of roastings 1～4 hour, obtains catalyst precursor;
C) gas mixture with air and water vapor activates, 200～300 ℃ of activation temperatures, and soak time 2～6 hours, the mol ratio of air and water vapor is 0.5～1.5: 1, obtains the catalyzer finished product.
2,, it is characterized in that polyphosphoric acid concentration is with P according to the preparation method of the described solid phosphoric acid catalyst of claim 1
2O
5Weight counts 70～85%.
3, according to the preparation method of the described solid phosphoric acid catalyst of claim 1, it is characterized in that containing silicon carrier is diatomite or silicon-dioxide.
4,, it is characterized in that of the form introducing of A component with corresponding oxide compound, oxyhydroxide or its decomposable salt according to the preparation method of the described solid phosphoric acid catalyst of claim 1.
5, according to the preparation method of the described solid phosphoric acid catalyst of claim 1, the heteropolyacid that it is characterized in that tungsten is silicotungstic acid, phospho-wolframic acid or its mixture, heteropolyacid aqueous solution weight concentration is 10%～and saturated.
6, according to the preparation method of the described solid phosphoric acid catalyst of claim 1, it is characterized in that adding extrusion aid talcum powder or sesbania powder before the extrusion, the extrusion aid add-on is 1～5% of a silicon carrier weight.
7, according to the preparation method of the described solid phosphoric acid catalyst of claim 1, it is characterized in that a value is 0.3～0.6, 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.
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|---|---|---|---|
| CNB021511691A CN1208130C (en) | 2002-12-11 | 2002-12-11 | Prepn of solid phosphoric acid catalyst for oligomerization of low-carbon olefine |
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|---|---|---|---|
| CNB021511691A CN1208130C (en) | 2002-12-11 | 2002-12-11 | Prepn of solid phosphoric acid catalyst for oligomerization of low-carbon olefine |
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|---|---|
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| CN1208130C true CN1208130C (en) | 2005-06-29 |
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| CN102744057B (en) * | 2011-04-20 | 2015-01-07 | 中国石油化工股份有限公司 | Preparation method of silicotungstic heteropoly acid loaded catalyst |
| EA201990391A1 (en) | 2016-08-04 | 2019-07-31 | Клариант Корпорейшн | SOLID PHOSPHORIC ACID CATALYSTS |
| CN111375433B (en) * | 2018-12-28 | 2023-02-03 | 中国石油化工股份有限公司 | Method for oligomerization of isobutene |
| CN112495404B (en) * | 2020-11-19 | 2022-07-12 | 万华化学集团股份有限公司 | Solid phosphoric acid catalyst, preparation method and recovery method of Saucy-Marbet reaction light component |
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