CN1155547C - Prepn of solid phosphoric acid catalyst for oligomerization of propylene - Google Patents
Prepn of solid phosphoric acid catalyst for oligomerization of propylene Download PDFInfo
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Abstract
The present invention relates to a preparation method of a propene oligomerization solid phosphoric acid catalyst. 72 to 88 wt% of polyphosphoric acid is prepared in a copper reaction kettle at the temperature of 120 to 180 DEG C, phosphate is prepared at the temperature of 150 to 230 DEG C, the phosphate is mixed with diatomite, and the mixture is squeezed for molding, dried, calcined and activated. Measured by the molar ratio, the catalyst contains the following general formula: SiAaBb(P2O5)c. (H2O)d, A is selected from at least one kind of boron, aluminum or indium, B is selected from at least one kind of titanium, zirconium, vanadium, niobium, chromium, molybdenum, magnesium, manganese or tungsten, a is from 0.2 to 1.5, b is from 0.01 to 0.2, c is from 1.0 to 2.0, and d is from 0.6 to 1.2. The material of the reaction kettle has strong polyphosphoric acid corrosion resistance, the production cost of the present invention is low, and the catalyst has superior activity and crushing resistant intensity.
Description
Technical field
The present invention relates to a kind of preparation method who is used for propene oligomerization solid phosphoric acid catalyst.
Background technology
Solid phosphoric acid catalyst (SPAC) is one of widely used catalyzer in the petrochemical industry, prepare tripolymer and tetrameric exemplary for olefin oligomerization, produce nonene and laurylene by propylene by an acidic catalyst oligomerisation, be characterized in that technological process is comparatively simple, technology maturation, the main difference of synthetic method is to use different catalyzer.According to relevant documents and materials, up to now, people are from propylene preparation tripolymer and tetrameric commercial catalysts, mostly still, continue to use the catalyzer of phosphoric acid series, the liquid phosphoric acid catalyzer that comprises California Research company, the pyrophosphate copper catalyst of Kellogg company, the phosphoric acid-quartzy catalyzer of Standard Oil company etc.Typical catalyzer is the solid phosphoric acid diatomite catalyzer by oligomerization of propene production polymer gasoline of American UOP company in the report.So far oligomerization of propene prepares tripolymer and tetrameric technology, uses this catalyzer mostly, and is described as patents such as US3112350, US3132109.
The preparation method of solid phosphoric acid catalyst mainly comprises pickling process and two kinds of methods of blending method.Early stage research adopts pickling process many, but because its manufacturing cycle is long, the catalyst reaction activity that makes is not high, is eliminated gradually; The catalyzer of blending method preparation is even owing to having mixing of materials, and the characteristics that catalyst activity is more satisfactory are main directions of this those skilled in the art's research.
In the blending method preparation process, people mainly take following measure: 1. improve material concentration, replace phosphoric acid with polyphosphoric acid in order to obtain high reactivity and high-intensity solid phosphoric acid catalyst.Polyphosphoric acid is meant P
2O
5Content surpasses the general name of 72% various phosphate mixtures, its acidity and strength of acid are higher than phosphoric acid far away, and in general, polyphosphoric acid concentration is high more, help improving the reactive behavior of catalyzer more, its preparation is to make phosphoric acid and Vanadium Pentoxide in FLAKES react formulated in reactor under certain temperature.2. in polyphosphoric acid, add auxiliary agent.With polyphosphoric acid and add component in reactor in 150～230 ℃ down reaction make polyphosphoric acid salt, evenly mixed with diatomite then, extruded moulding.Above-mentioned two kinds of reactions all are the bigger reactions of thermal discharge, for avoiding out of control because of the rapid temperature of reaction of material, need control reaction feed rate in the reaction, and the reaction times is longer.Under at high temperature, than long reaction times condition, polyphosphoric acid is very strong to the corrodibility of reactor, than high times of phosphoric acid, thereby cause this method in many batches, long-term industrial production, raw material is serious to the extent of corrosion of reactor, need the periodic replacement reactor, to guarantee the producing safety of normally carrying out with operator, make this method to equipment material have relatively high expectations, the production cost height.
In the existing document, about the preparation solid phosphoric acid catalyst reactor material aspect report seldom, patent CN1049373A discloses a kind of phosphoric acid/active carbon catalyst and coincidence process, this catalyzer is that the processed active carbon carrier is immersed in the technical pure phosphoric acid, flooded reflux 2～8 hours in 100～110 ℃, through filtering, drying activates and makes the catalyzer finished product.This catalyzer is 130～230 ℃ of temperature of reaction, reaction raw materials air speed 2.5～5.0hr
-1, under reaction pressure 2.0～6.0MPa condition, the peak rate of conversion of alkene oligomerization reaction is 72.44%, crush strength is on the low side, have only 170 newton/centimetre
2, catalyst stability is relatively poor.The document does not relate to the equipment material problem.
Chinese patent 97106216.1 (CN1187388A) discloses a kind of propene oligomerization solid phosphate catalyst, 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 or their mixture; C=B, Sb, Bi or their mixture; A, b, c, d equal the atomicity of 1 o'clock respective element for the A component.This catalyzer adopts the blending method preparation: component B and C are joined in the polyphosphoric acid, make phosphoric acid salt 120～230 ℃ of reactions, the material that obtains behind the extruded moulding, obtains catalyzer finished product through super-dry, roasting, activation at 140～230 ℃ of following and A component blends.This catalyzer is 200 ℃ of temperature of reaction, reaction raw materials air speed 2.0hr
-1, carry out propylene oligomerization under the reaction pressure 4.0MPa condition, the propylene peak rate of conversion is 82.1%, the axial crushing strength of catalyzer be 730 newton/centimetre
2Preparation of catalysts does not relate to the equipment material problem in the document.
Summary of the invention
Technical problem to be solved by this invention is on the prior art basis, a kind of preparation method of propene oligomerization solid phosphoric acid catalyst is provided, the anti-polyphosphoric acid corrodibility of reactor material that this method is used is strong, and production cost is low, and the catalyzer of preparation has higher activity and crush strength.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of propene oligomerization solid phosphoric acid catalyst, phosphoric acid and Vanadium Pentoxide in FLAKES are made polyphosphoric acid in 120～180 ℃ in reactor, make mixed phosphate to wherein adding component A and B in 150～230 ℃ then, keep this temperature of reaction, above-mentioned phosphoric acid salt and diatomite are mixed, through extruded moulding, in 150～300 ℃ of dryings 1～5 hour, in 400～600 ℃ of roastings 1～4 hour; Activate with water vapor and Air mixing gas, 150～300 ℃ of activation temperatures, soak time 1～6 hour, air: the mol ratio of water vapor is 0.5～1.5: 1; Wherein polyphosphoric acid contains Vanadium Pentoxide in FLAKES 72～88% by weight; Catalyzer is formed: SiA
aB
b(P
2O
5)
c(H
2O)
d, A is selected from least a in boron, aluminium or the indium in the formula; B is selected from least a in titanium, zirconium, vanadium, niobium, chromium, molybdenum, magnesium, manganese or the tungsten; A=0.2～1.5, b=0.01～0.2, c=1.0～2.0, d=0.6～1.2, a, b, c, d equal the mole number of 1 o'clock corresponding component for the Si atom; The reactor material is a copper.
In the technique scheme, A preferably is selected from least a in boron or the aluminium; B preferably is selected from least a in titanium, zirconium, niobium, magnesium or the manganese; The a preferable range is 0.6～1.2, and the b preferable range is 0.03～0.10, and the c preferable range is 1.2～1.8, and the d preferable range is 0.7～1.0; A and B component are introduced with the form of oxide compound, oxyhydroxide or soluble salt; Described copper is red copper or electrolytic copper; Electrolytic copper preferably.
Among the solid phosphoric acid catalyst preparation method, reactor is main key equipment.The raw material polyphosphoric acid is as the liquid high strength acid, and is at high temperature serious to equipment corrosion, needs periodic replacement equipment, makes this method production cost height.Therefore, the inventor selects multiple metallic substance for use, under 200 ℃ of conditions, as reaction medium, does the acid-resistant corrosion test with polyphosphoric acid.In selected materials, what corrosion resistance nature was best is T-1 steel (Shanghai Inst. of Materials's development), but it costs an arm and a leg; Next is electrolytic copper and red copper, moderate cost; The stainless steel erosion resistance that contains different components is relatively poor relatively, and price is than copper product height, so slave unit investment and processing complexity consider that the inventor selects for use red copper or electrolytic copper as the reactor material, both economical, its facility investment expense only is 1/10th of a T-1 steel.Criticize the Preparation of Catalyst test through hundreds of, prove the corrosion that can withstand polyphosphoric acid under the high temperature, show that in the solid phosphoric acid catalyst preparation process it is feasible selecting for use red copper or electrolytic copper to do the reactor material.
The raw material polyphosphoric acid that the inventive method is used is that phosphoric acid and Vanadium Pentoxide in FLAKES are made in 120～180 ℃ of reactions, because Vanadium Pentoxide in FLAKES dissolution process thermal discharge is bigger, feed liquid is sharply heated up, influence the phosphorus content of catalyzer for fear of the Vanadium Pentoxide in FLAKES distillation, during operation, earlier phosphoric acid is put in the reactor, add Vanadium Pentoxide in FLAKES then, the control feed rate, keep temperature of reaction, treat that Vanadium Pentoxide in FLAKES is reinforced to finish, continued stirring reaction 4～5 hours, dissolve fully until material, contained the polyphosphoric acid of Vanadium Pentoxide in FLAKES 72～88% by weight.
With the preparation polyphosphoric acid in the copper reactor, under electronic stirring, add the A component earlier, add the B component again, make the polyphosphate mixture, the control feed rate 150～230 ℃ of reactions, temperature of reaction is no more than 230 ℃, mediate with dry diatomite then, extruded moulding obtains the catalyzer finished product through super-dry, roasting, activation.
The solid phosphoric acid catalyst of the inventive method preparation is specially adapted to propylene oligomerization and produces nonene and laurylene, also is applicable to C
3Or/and C
4Alkene oligomerization prepares C
6～C
16Alkene, the superimposed production stop bracket gasoline of C 4 olefin, the iso-butylene dimerization is produced technologies such as isooctene, all can obtain gratifying effect.
The catalyzer crushing strength test of the present invention preparation adopts existing enterprise's standard method to measure, and testing tool is the electronic intensity measuring device of DL-II, and the catalyzer crushing strength of mensuration is the broken power of axial compression resistance that unit surface can be born, unit be newton/centimetre
2
The catalyst activity evaluation of the present invention's preparation is carried out in fixed-bed reactor, and 100 milliliters of catalyzer of filling in the device adopt propylene as reaction raw materials, and propane is made thinner, raw material propylene concentration 40～60% (quality), and all the other are propane.180～220 ℃ of temperature of reaction, reaction pressure 3.0～6.0MPa, liquid volume air speed 1～5 hour
-1Under the processing condition, raw material propylene is contacted with solid phosphoric acid catalyst propylene oligomerization takes place.
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, according to alkene, alkane quality percentage composition in GB/T3392-82 (the mensuration vapor-phase chromatography of hydrocarbon impurities in propylene) determination and analysis raw material and the tail gas, calculate olefin conversion thus, the purpose selectivity of product.Wherein olefin conversion, purpose selectivity of product are defined as follows:
The present invention prepares the method for solid phosphoric acid catalyst, adopt copper as the reactor material, anti-polyphosphoric acid corrodibility is strong under the pyroreaction condition, and the facility investment expense is low, prepare 200 batches altogether and amount to 28 tons of solid phosphoric acid catalysts, the reactor bottom still can continue to use not obviously by the acid corrosion phenomenon; And use stainless steel (Cr
18Ni
12Mo
2The Ti alloy) reactor of material prepares 100 batches and amounts to 14 tons of solid phosphoric acid catalysts, can be observed reactor bottom, sidewall by the obvious corrosion phenomenon of acid, use if continue aborning, have hidden danger, the reactor that need more renew makes production cost higher.
Preparation of catalysts method of the present invention is selected from boron, aluminium or the indium at least a by adding in the P-Si of conventional solid phosphoric acid catalyst system, improved activity of such catalysts, has obviously improved catalyzer extrusion, moulding process; Simultaneously by in P-Si-B (Al, In) system, introducing at least a component that is selected from titanium, zirconium, vanadium, niobium, chromium, molybdenum, magnesium, manganese or the tungsten, under described Preparation of Catalyst condition, formed mixture with certain molecular structure, this mixture is through high-temperature roasting, the intermolecular synergy of each element has further improved catalyst activity, makes the catalyzer of preparation have very high crush strength simultaneously, anti-argillization ability is strong, long service life.For example the embodiment of the invention 2 catalyzer are used for propylene oligomerization and produce nonene and laurylene, and propylene conversion can reach 84.5%, nonene selectivity 63.0%, laurylene selectivity 22.3%, crush strength be 980 newton/centimetre
2And in the comparative example 1 by comparison, Preparation of Catalyst does not add any B component, and catalyzer consists of the P-Si-B system, and this catalyzer is used for propylene oligomerization and produces nonene and laurylene, propylene conversion 78%, and crush strength 580 newton/centimetre
2, its activity and intensity are starkly lower than the catalyzer index of the inventive method preparation.
Below by embodiment the present invention is specifically addressed.
Embodiment
[embodiment 1]
The metallic substance corrosion test of anti-the polyphosphoric acid.
Get the metal material sheet of same size, its weight of weighing before the test impregnated in concentration respectively then with P
2O
5Weight is counted in 83.5% the polyphosphoric acid, 200 ℃ of dipping temperatures, and dipping time 30 days takes out metal material sheet, weighs respectively, is converted into corrosion thickness unit.The results are shown in table 1.Find out that from measuring result the anti-polyphosphoric acid corrodibility of T-1 steel is the strongest, but it costing an arm and a leg, is red copper and electrolytic copper secondly, and the stainless steel erosion resistance is relatively poor.
Table 1
| Metallic substance | Corrosion thickness (centimetre/year) |
| The T-1 steel | 0.202 |
| Electrolytic copper | 0.406 |
| Red copper | 0.461 |
| The 10# steel | 0.711 |
| Stainless steel (Cr17Ni14Mo2 alloy) | 0.806 |
| Stainless steel (Cr18Ni12Mo2Ti alloy) | 2.87 |
[embodiment 2]
The preparation of raw material polyphosphoric acid:
43.8 kilogram of 83.5% (weight) polyphosphoric acid joined in the red copper reactor, be warming up to 100 ℃, add 58.2 kilograms of Vanadium Pentoxide in FLAKESs, control reaction temperature is at 130～150 ℃, treating that Vanadium Pentoxide in FLAKES is reinforced finishes, continued stirring reaction 4～5 hours, and dissolved fully, contained the polyphosphoric acid of Vanadium Pentoxide in FLAKES 83.5% by weight until material.
The solid phosphoric acid catalyst preparation:
In the polyphosphoric acid of above-mentioned preparation, under electronic stirring, add Niobium Pentxoxide respectively, 19.8 kilogram boric acid, control reaction temperature is at 180～200 ℃, make the polyphosphate mixture, simultaneously 25.6 kilograms of dry diatomite are added in the kneading machine, add the polyphosphate mixture, mediated 4 minutes, obtain viscosity bulk material, extruded moulding was in 170 ℃ of dryings 2 hours, in 550 ℃ of roastings 1.5 hours, activate the activating process condition with water vapor and Air mixing gas: 200 ℃ of activation temperatures, soak time 3 hours, air: the mol ratio of water vapor is 1.4: 1, obtains the catalyzer finished product.The solid phosphoric acid catalyst that makes is formed:
Si
1B
0.8Nb
0.05(P
2O
5)
1.6·(H
2O)
0.8
Use the reactor of material as red copper, according to above-mentioned preparation condition, prepare 200 batches of 28 tons of solid phosphoric acid catalysts altogether, reactor bottom, sidewall do not have obviously by the acid corrosion phenomenon, still can continue to use.
According to aforesaid evaluating catalyst process, the catalyzer that example 2 is prepared is used for propylene oligomerization, estimates processing condition: 200 ℃ of temperature of reaction, pressure 4.0MPa, liquid volume air speed 2.0 hours
-1, raw material propylene concentration 50% (quality).The evaluating catalyst result: propylene conversion 84.5%, nonene selectivity 63.0%, laurylene selectivity 22.3%, catalyzer crush strength 980 newton/centimetre
2
[embodiment 3]
The preparation of raw material polyphosphoric acid:
According to the preparation condition of example 2, difference: the reactor material is an electrolytic copper, makes 100 kilograms of polyphosphoric acid, contains Vanadium Pentoxide in FLAKES 80% by weight.
The solid phosphoric acid catalyst preparation:
The polyphosphoric acid of above-mentioned preparation is under electronic stirring, add zirconium white, 22.0 kilograms of boric acid respectively, 170～200 ℃ of control reaction temperature are made the polyphosphate mixture, simultaneously 26.5 kilograms of dry diatomite are added in the kneading machine, add the polyphosphate mixture, mediated 4 minutes, and obtained viscosity bulk material, extruded moulding, in 200 ℃ of dryings 1 hour, in 500 ℃ of roastings 2 hours; Activate the activating process condition with water vapor and Air mixing gas: 250 ℃ of activation temperatures, soak time 4 hours, air: the mol ratio of water vapor is 1.4: 1, obtains the catalyzer finished product.The solid phosphoric acid catalyst that makes is formed:
Si
1B
1.0Zr
0.04(P
2O
5)
1.4·(H
2O)
0.9
Use the reactor of material as electrolytic copper, according to example 3 preparation conditions, prepare 200 batches of 29 tons of solid phosphoric acid catalysts altogether, reactor bottom, sidewall do not have obviously by the acid corrosion phenomenon, still can continue to use.
According to aforesaid evaluating catalyst process, the catalyzer that example 1 is prepared is used for propylene oligomerization, estimates processing condition: 200 ℃ of temperature of reaction, pressure 4.0MPa, liquid volume air speed 2.0 hours
-1, raw material propylene concentration 45% (quality).The evaluating catalyst result is: propylene conversion 81.2%, and nonene selectivity 61.0%, laurylene selectivity 23.1%, catalyzer crush strength 950 newton/centimetre
2
[comparative example 1]
According to the preparation method of embodiment 1, will contain P by weight
2O
582% polyphosphoric acid 1000 grams with 193 gram acid reactions, do not add any B component, knead in kneading machine evenly with the dry diatomite of 258 grams then.The catalyzer that makes is formed:
Si
1B
0.75(P
2O
5)
1.4·(H
2O)
0.8
Catalyzer materialization test result: crush strength 580 newton/centimetre
2
Use the evaluation method identical, evaluating catalyst result: propylene conversion 78%, nonene selectivity 62%, laurylene selectivity 16%, nonene and laurylene overall selectivity 78% with embodiment 1.
[comparative example 2]
Use the reactor of material, prepare 100 batches of 14 tons of solid phosphoric acid catalysts altogether, can be observed the reactor bottom, sidewall has obviously by the acid corrosion phenomenon according to the reaction conditions of embodiment 2 as stainless steel (Cr18Ni12Mo2Ti alloy).
Claims (6)
1, a kind of preparation method of propene oligomerization solid phosphoric acid catalyst, phosphoric acid and Vanadium Pentoxide in FLAKES are made polyphosphoric acid in 120～180 ℃ in reactor, make mixed phosphate to wherein adding component A and B in 150～230 ℃ then, keep this temperature of reaction, above-mentioned phosphoric acid salt and diatomite are mixed, through extruded moulding, in 150～300 ℃ of dryings 1～5 hour, in 400～600 ℃ of roastings 1～4 hour; Activate with water vapor and Air mixing gas, 150～300 ℃ of activation temperatures, soak time 1～6 hour, air: the mol ratio of water vapor is 0.5～1.5: 1; It is characterized in that polyphosphoric acid contains Vanadium Pentoxide in FLAKES 72～88% by weight; Catalyzer is formed:
SiA
aB
b(P
2O
5)
c(H
2O)
d, A is selected from least a in boron, aluminium or the indium in the formula; B is selected from least a in titanium, zirconium, vanadium, niobium, chromium, molybdenum, magnesium, manganese or the tungsten; A=0.2～1.5, b=0.01～0.2, c=1.0～2.0, d=0.6～1.2, a, b, c, d equal the mole number of 1 o'clock corresponding component for the Si atom; The reactor material is a copper.
2,, it is characterized in that A is selected from least a in boron or the aluminium according to the preparation method of the described propene oligomerization solid phosphoric acid catalyst of claim 1; B is selected from least a in titanium, zirconium, niobium, magnesium or the manganese.
3,, it is characterized in that a=0.6～1.2, b=0.03～0.10, c=1.2～1.8, d=0.7～1.0 according to the preparation method of the described propene oligomerization solid phosphoric acid catalyst of claim 1.
4,, it is characterized in that the form introducing of A and B component with oxide compound, oxyhydroxide or soluble salt according to the preparation method of the described propene oligomerization solid phosphoric acid catalyst of claim 1.
5,, it is characterized in that described copper is red copper or electrolytic copper according to the preparation method of the described propene oligomerization solid phosphoric acid catalyst of claim 1.
6,, it is characterized in that described copper is electrolytic copper according to the preparation method of the described propene oligomerization solid phosphoric acid catalyst of claim 5.
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|---|---|---|---|
| CNB011262842A CN1155547C (en) | 2001-07-20 | 2001-07-20 | Prepn of solid phosphoric acid catalyst for oligomerization of propylene |
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|---|---|---|---|
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| CN1155547C true CN1155547C (en) | 2004-06-30 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9403149B2 (en) | 2011-09-21 | 2016-08-02 | Clariant Corpoation | Promoted solid phosphoric acid catalysts and methods of use |
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|---|---|---|---|---|
| CN102895982B (en) * | 2012-09-28 | 2017-10-13 | 彤程化学（中国）有限公司 | Catalyst roasting-shaping Liang rotation rotary kilns |
| CN105618092B (en) * | 2015-02-15 | 2018-06-08 | 彤程化学（中国）有限公司 | Solid phosphoric acid catalyst preparation method orients feeder and its application for the vibrating type fine powder of this method |
| CN110935434A (en) * | 2019-12-09 | 2020-03-31 | 北京石油化工学院 | Catalyst for preparing nonene and dodecene by propylene oligomerization and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9403149B2 (en) | 2011-09-21 | 2016-08-02 | Clariant Corpoation | Promoted solid phosphoric acid catalysts and methods of use |
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Granted publication date: 20040630 Termination date: 20110720 |