CN102895982A - Catalyst roasting-shaping dual-purpose rotary kiln - Google Patents
Catalyst roasting-shaping dual-purpose rotary kiln Download PDFInfo
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- CN102895982A CN102895982A CN2012103663572A CN201210366357A CN102895982A CN 102895982 A CN102895982 A CN 102895982A CN 2012103663572 A CN2012103663572 A CN 2012103663572A CN 201210366357 A CN201210366357 A CN 201210366357A CN 102895982 A CN102895982 A CN 102895982A
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Abstract
The invention relates to two work procedures of roasting and shaping in a preparation technology of an SPAC (solid phosphoric acid catalyst). The SPAC is applied to reactions including low-carbon olefin oligomerization, allyl benzene alkylation and the like. According to the conventional preparation technology of the SPAC, the roasting procedure and the shaping procedure are respectively carried out, wherein the roasting procedure adopts a static mode, while materials can not be completely and uniformly heated; and the a crusher is adopted for shaping, so that the yield of finished products is low, the loss of crushing is high, broken granules and powder are formed, and 'memory'cracks exist in the granules. The inventor provides a conception of critical bar length, and defines a particle breakage probability function as zi= K* (Li-Lcri) alpha; and during the rotary process of the kiln, bar-shaped materials with same mass fall from the top end of an internal shovelling plate, collide with the bottom of the kiln, and are broken, then the broken bars have consistent lengths, and finally the roasting-shaping dual-purpose rotary kiln is designed. The obtained SPAC granules have small lengths and small strength distribution, so that the conversion rate of the catalytic reaction and the selectivity of oligomers are improved, the argillization tendency is reduced, and the running service life is prolonged. The lengths of the granules of a product provided by the invention depend on the effective radius of the roasting kiln (rbs). The catalyst roasting-shaping dual-purpose rotary kiln can be implemented in the industry.
Description
Technical field
The invention belongs to the solid phosphoric acid catalyst preparation field, be specifically related to a kind of catalyst roasting-shaping Liang rotation rotary kiln, particularly a kind of calcining process and trimming of solid phosphoric acid catalyst preparation.
Background technology
Catalyst for oligomerization has homogeneous phase and heterogeneous two classes.Sulfuric acid, phosphoric acid and so on homogeneous catalyst, although the speed that responds is high and the conversion ratio advantages of higher, product separation difficulty and have a large amount of waste liquids the problem such as need to process has not had commercial plant basically in application; Heterogeneous catalyst for oligomerization mainly comprises: zeolite type solid acid catalyst, means of nonzeolitic solid acid catalyst and other loaded catalysts.The support type catalyst for oligomerization roughly can be classified as 3 classes: the one, and with BF
3Load Lewis acid or super acids catalyst for oligomerization for representative; Another kind of is carried metal catalyst for oligomerization take nickel, iron as representative.Uop Inc. all made extensive work in above-mentioned two fields, had applied for many patents; The 3rd class is the most widely solid phosphoric acid catalyst (SPAC) of commercial Application.Uop Inc. and Shanghai Petroleum Chemical Engineering Institute all development and production commodity SPAC.
Commodity SPA-1, SPA-2 and the SPA-5 of Uop Inc., existing 70 years commercial Application history has the above commercial plant of 300 covers to use for a long time the SPAC of Uop Inc. in the world; SINOPEC Shanghai Petroleum Chemical Engineering Institute bore country's " eight or five brainstorm project "-" oligomerization of propene prepares nonene and synthetic nonyl phenol " from 1986, be engaged in the research of propene oligomer catalyst and oligomerization process, developed the T-49 solid phosphoric acid catalyst, beginning was in Lanzhou Oil Refinery (now being Petro China Lanzhou Petrochemical) commerical test and commercial Application in 1997, develop again the T-99 catalyst in 1999, further improved reactivity and the anti-argillization ability of catalytic oligomerization.
Since the pioneering solid phosphoric acid catalyst of nineteen thirties American UOP company is used for alkene oligomerization, still adopted this catalyst from propylene production its tripolymer and the tetramer so far.Yet because the easy argillization of solid phosphoric acid catalyst causes the not long disadvantage of catalyst life to exist all the time, so people focus on improvement preparation technology in the active structure and exploitation new support of this catalyst of research.
The strict condition of controlling crystallization steps in the catalyst preparation process can obtain satisfied silicon phosphate crystalline content in the US Patent No. 4946815, thereby improves the life-span of SPA catalyst.This is disclosed first invention after 1972 of the SPA of Uop Inc. catalyst patented technology.The SPA catalyst of this invention usefulness is approximately to make under 170 ℃ the polyphosphoric acid of heat (contain P
2O
582%) and diatomite mix, phosphorus acid content wherein is with P
2O
5Meter, mass fraction be best greater than 80%, and the mixture outward appearance is for from damp slightly to almost doing, but are plastic during extrusion.Make unformed extrusion modling semi-products crystallization after extrusion, the pelletizing, thereby obtain the catalyst finished product.The key of invention is temperature, steam addition and the crystallization time of controlling crystallizing process device therefor.These factor relations siliceous phosphatic type and quantity in the catalyst finished product.
Relate among the China Patent No. CN1960956A in the method that is used for the lower polyolefins raw material, raw material is contacted with the second catalyst that (b) comprises solid phosphoric acid with (a) first crystalline molecular sieve catalyst under oligomeric condition.This first and second catalyst can be included in the different reactors or as the different bed in the single reactor.Be that olefin feedstock contacted first molecular sieve catalyst before the contact solid phosphoric acid catalyst.The stability ratio of the method is high five times when using the SPA catalyst separately.Catalyst can get out from reactor when EO.The water that need not costliness commonly used in this type of reactor that adopts separately the SPA catalyst sprays.
A kind of preparation method for propene oligomerization solid phosphoric acid catalyst has been proposed among the China Patent No. CN1187387A, at first five phosphorous oxide and phosphoric acid are made polyphosphoric acids under 120-230 ℃, with co-catalyst after making phosphate under 120-230 ℃ with the diatomite blend, behind the extruded moulding, at the 100-250 ℃ of lower dry 1-10h that processes, then with 500-650 ℃ of condition under in Muffle furnace roasting 0.5-24h, adopting air, the gaseous mixture of steam process and catalyst, the catalyst that this preparation method makes has active high, intensity is high, water resistance is good, and the characteristics that rate of wear is little can be used in the industrial production.
In the SPAC preparation process, roasting, two operations of shaping were carried out respectively, had following shortcoming in the past:
(1) material is admitted to disintegrating machine and carries out broken shaping after calcining process, the problem such as particle produces a large amount of particles and dust when fragmentation, and exists the product abrasion rate high, and broken loss is large, and yield is low;
(2) traditional calcining process adopts static mode, tunnel cave no matter, and perhaps all there are the material to be machined defectives inhomogeneous, that the roasting degree is different of being heated in Muffle furnace, and causes product intensity inhomogeneous;
(3) product of roasting adopts the disintegrating machine shaping, and there is residual slight crack (being commonly called as the memory slight crack) in catalyst granules, and the particle of intensity difference, crackled particle are easily broken in transportation, the loading process; The easy argillization of particle in the use procedure causes that pressure drop of column rises.
For addressing the above problem, the inventor has designed the double function operation that carries out at apparatus for rotating: roasting-shaping.The SPAC particle length that obtains and intensity distributions is narrow, product yield is high, and improved the catalytic reaction conversion ratio and oligomer selective, reduced catalyst argillization tendency, prolong running life.The present invention can industrial realization.
Summary of the invention
The invention belongs to roasting and two operations of shaping in solid phosphoric acid catalyst (SPAC) preparation field.This catalyst is applied to low-carbon alkene oligomerisation reaction, propenyl benzene alkylated reaction.The solid phosphoric acid catalyst preparation, through 5 operations that are closely related: the boric acid complex salt of polyphosphate preparation (reaction), poly phosphorus boric acid complex salt preparation (kneadings), continuity poly phosphorus prepares (homogenizing), moulding and drying, acquisition catalyst firing precursor.Traditional subsequent handling is: roasting, shaping, activation and screening obtain finished product SPAC.Roasting is that unformed silicophosphate is converted into crystal type salt; Shaping is to make the different catalyst of length become the particle that length reaches unanimity.
The object of the invention is to provide the difunctional operation of carrying out continuously among a kind of solid phosphoric acid catalyst preparation technology: roasting and particle shaping, obtain catalyst precarsor homogeneous, diameter 3mm～7mm through reaction, kneading, homogenizing, moulding, dry 5 operations, obtain finished product through roasting and particle shaping operation, activation and preliminary abrasion operation subsequently.
Another object of the present invention is to provide roasting, two operations of shaping to adopt difunctional equipment to realize: difunctional roasting-shaping two rotation rotary kiln, realize two not operations of same-action at same equipment.
Wherein said roasting-shaping Liang Yong rotation rotary kiln internal diameter according to the catalyst granules length requirement, is depended on structural parameters α (=f (r
Bs)), r
BsBe the calcining kiln cylinder internal diameter, adopt the definite difunctional roasting of half experiment and semi-analytic method-shaping kiln internal diameter r
Bs=φ 1.8m～2.5m.
Described roasting-shaping Liang Yong rotation rotary kiln is the difunctional roasting of flight formula-shaping Liang rotation rotary kiln, cylindrical shell forms by preheating, roasting and 3 zones of cooling, require total length 〉=20m, in the cylinder 120 ° of flights are set, arrange along 60 ° of dislocation of circumference, every flight length is 0.3～1.2m, and the flight width is (1/10～1/6) .r
Bs
Described roasting-shaping Liang Yong rotation rotary kiln arranges 3～10 points for measuring temperature along roasting-shaping Liang Yong rotation rotary kiln length at the adherent place of inner barrel, measures respectively preheating section, furnace zone and cooling section temperature, uses the wireless temperature measurement assembly.
Among the present invention, the inventor proposes: " critical long concept of same diameter physical property circle of the same race strip-shaped materials contour whereabouts fracture " defined above-mentioned bar fracture probability function: ζ
i=k (L
i-L
Cri)
α
In difunctional revolution calcining kiln of the present invention, in the time of the roasting of material experience, along with the cylindrical shell rotation, the cylinder strip precursor that diameter is identical is fixed on the knuckle flight of cylinder inboard wall and takes up, also promotes thereupon at the bottom of cylinder, and gradually from the landing of flight front end.From the cylindrical shell cross-sectional view, the catalyst precarsor of landing falls as " curtain of rain ", the whereabouts precursor fractures with being positioned at the cylinder body bottom collision, particle length after fractureing and precursor the original length are irrelevant, and meet the fracture probability that the inventor proposes: longer material is more disconnected, and the probability that namely fractures is large; Short material is easy fracture not, and probability is little; Bar is long be the particle of some critical values, and falling not in this kind condition can fracture, and probability is zero.Make the material that enters the enough kilns of cylindrical shell length, stove, no matter take up, fall through how many times, the product length of acquisition reaches unanimity.The fracture probability definition:
ζ
i＝k·(L
i-L
cri)
α (1)
In the formula: ζ
i: the fracture probability of bar i, %;
α: the breaking strength index relevant with frame for movement, α=f (r), r are the effective radiuses of cylindrical shell;
K: the parameter relevant with the bar nature, k=f (R
P/W); R
P/WPhosphorus, the water ratio of material;
L
i: the length of bar i;
Subscript i=1,2,3 ..., n, granule number n are the large quantity of corresponding probability;
L
Cri: the critical length of bar is under this broken condition, the bar length that fall, collision is no longer ruptured;
According to above-mentioned concept and fracture probability: in the turning course of kiln, particle falls from the flight top, with the bottom bump, causes the bar length of fracture to reach unanimity.The inventor has designed the double function operation that carries out at apparatus for rotating: roasting-shaping.The SPAC particle length that obtains and intensity distributions is narrow, product yield is high, and improved the catalytic reaction conversion ratio and oligomer selective, reduced catalyst argillization tendency, prolong running life.Product particle length of the present invention depends on calcining kiln effective radius r
BsThe present invention can industrial realization.
The present invention has improved SPAC running life and olefin conversion when having improved SPAC product yield and running effect.The present invention can industrial implementation.
Description of drawings
Fig. 1 is that material is in calcining kiln cross sectional representation of the present invention.Can see that along with kiln rotation, flight is taken up precursor granules to come from the bottom, particle drops to bottom of cylinder from the landing of flight top, bumps with the particle of bottom and ruptures.
The specific embodiment
Obtain 5 operations that are closely related that have of catalyst firing precursor in solid phosphoric acid catalyst (SPAC) preparation process: polyphosphate preparation (reaction), poly phosphorus boric acid complex salt preparation (kneading), the preparation of continuity polyphosphoric acids boric acid complex salt (homogenizing), moulding and drying.The tradition subsequent handling is: roasting, shaping, activation and screening obtain finished product SPAC.
The catalyst firing precursor is come subsequent handling with " memory " of 5 process operations of front.At first at swinging flight roasting-shaping kiln, carry out roasting, and it is long that catalyst precarsor is broken into the bar of regulation.
The SPAC raw materials that the present invention uses sees Table 1, and the product quality of acquisition and Comparative Examples quality see Table 2.Be used for SPAC firing precursor of the present invention from drying process, major traits: diameter 5mm～6mm; Be uneven in length, be the even cylindrical bars of 10mm～80mm.
Table 1 embodiment raw material physicochemical property
Catalyst oligomerisation reaction activity rating carries out at laboratory single tube fixed bed reactors experimental rig, and reactor loads the SPAC particle that is broken into the 2mm size, volume 10mL; The condition of the listed embodiment of table 2 and contrast test: raw material butene content 46.11%, basic nitrogen compound content 1.2ppm, alkadienes and alkynes content 2.1%; Reactor feed air speed (v) 2h
-1, 200 ℃ of reaction temperatures, reaction pressure 4.8MPa.Test raw material gas and tails assay use 102 gas-chromatographies to carry out online, device steady running 20h, and the reactor outlet tails assay obtains the hydrocarbon composition that represents with mole fraction, calculates the mixed butene conversion ratio of this reaction, as the oligomerisation reaction activity value.The butene conversion calculating formula:
x
∑C4＝1-[(n
C4H8·n
0C4H10)/(n
C4H10·n
0C4H8)]×100 (3)
In the formula: x
∑ C4Be mixed butene conversion ratio, %; n
0C4H8, n
0C4H10Be respectively the molar concentration of butylene and butane in the raw material, n
C4H8, n
C4H10Be respectively the molar concentration of butylene and butane in the tail gas.
Embodiment
The present invention the dual-purpose rotary kiln of industrial flight formula roasting-shaping (kiln cylinder body length 29m, interior through r
Bs=φ 2.0m) implements.Kiln cylinder body tilts 2.5%, and cylinder inboard wall all has 120 ° of knuckle flights, and every block length 0.4m, width are (1/8) .r
BsAlong 24 ° of settings of circumference, 15 every group; Adjacent flight staggers 12 °.The calcining kiln that uses is external-heat, and fuel is bituminous coal; Formed by preheating section, furnace zone, cooling section; The kiln inwall arranges temperature element, measures each section temperature.
The precursor of sending here with conveyer belt from drying process adds the kiln body continuously from the roasting kiln hood, and calcining kiln cylindrical shell speed of gyration is 0.25r/min, and the roast area temperature of calcining kiln is controlled at 590 ℃, time of staying 80min; Together with preheating, cooling, material total residence time in calcining kiln is 2.5h.The catalyst granules that leaves calcining kiln falls into circular reciprocating sieve from the kiln tail, and compass screen surface is 50 mesh standard sieves, removes the storage bin that the later product of roasting of fine particle and powder enters activation procedure,
Fig. 1 is that material is in calcining kiln cross sectional representation of the present invention.Can see that flight is taken up precursor granules to come from the bottom along with the rotation of kiln, stove, particle drops to bottom of cylinder from the landing of flight top, bumps with the particle of bottom and ruptures.
Implement test and carry out continuously at the commercial scale device, get wherein the 24h service data and finished product as the embodiment sample.Operating condition: calcining kiln feeds intake from drying process, inventory: 300kg/h, and 150 ℃ of temperature enter kiln hood continuously; Data acquisition period, preheating section temperature rise to 587 ℃ of 577 ℃, furnace zone mean temperature from 150 ℃,, the cooling section temperature drops to 170 ℃ by 585 ℃, enters the activation procedure storage bin from the kiln afterproduct after rotary strainer separates particle and powder.The 24h roasting 7200kg that always feeds intake, 24h collects and obtains 157kg crushed particles and powder under the rotary strainer, average 4.13kg/h, roasting-trimming yield 97.8%.
The outturn sample that above-mentioned experiment obtains enters activation procedure, and activation products are through 50 order rotary strainers, and the upper strata obtains finished catalyst, the 100g that per hour keeps sample, and 24h obtains sample 2400g, therefrom sample analysis, test, the product quality analysis of acquisition the results are shown in Table 2.The contrast sample is the production piece that Uop Inc. offers domestic certain petro-chemical corporation, and test, evaluation are undertaken by laboratory of the present invention, and the result lists file names with, and is for reference.
Table 2 embodiment SPAC and certain company's product quality are relatively
[1] comparative sample is UOP SPA-2, and industrial products are by this researcher practical measurement;
Claims (5)
1. the difunctional operation of carrying out continuously among the solid phosphoric acid catalyst preparation technology: roasting and particle shaping, obtain catalyst precarsor homogeneous, diameter 3mm～7mm through reaction, kneading, homogenizing, moulding, dry 5 operations, obtain finished product through roasting and particle shaping operation, activation and preliminary abrasion operation subsequently.
2. difunctional operation according to claim 1 is characterized in that described roasting, two operations of particle shaping adopt difunctional equipment to realize: difunctional roasting-shaping two rotation rotary kiln, realize two not operations of same-action at same equipment.
3. difunctional operation according to claim 2 is characterized in that the internal diameter of described roasting-shaping Liang Yong rotation rotary kiln according to the catalyst granules length requirement, depending on structural parameters α (=f (r
Bs)), r
BsBe the calcining kiln cylinder internal diameter, adopt the definite difunctional roasting of half experiment and semi-analytic method-shaping Liang Yong rotation rotary kiln internal diameter r
Bs=φ 1.8m～2.5m.
4. according to claim 2 or 3 described difunctional operations, it is characterized in that described roasting-shaping Liang Yong rotation rotary kiln is the difunctional roasting of flight formula-shaping Liang rotation rotary kiln, cylindrical shell forms by preheating, roasting and 3 zones of cooling, require total length 〉=20m, in the cylinder 120 ° of flights are set, arrange along 60 ° of dislocation of circumference, every flight length is 0.3～1.2m, and the flight width is (1/10～1/6) r
Bs
5. described difunctional operation one of according to claim 2～4, it is characterized in that described roasting-shaping Liang Yong rotation rotary kiln is along roasting-shaping Liang Yong rotation rotary kiln length, at the adherent place of inner barrel 3～10 points for measuring temperature are set, measure respectively preheating section, furnace zone and cooling section temperature, use the wireless temperature measurement assembly.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103743228A (en) * | 2014-01-17 | 2014-04-23 | 中国大唐集团科学技术研究院有限公司 | Industrial rotary kiln |
| CN104971783A (en) * | 2015-06-18 | 2015-10-14 | 江西昌宁化工有限责任公司 | Continuous technology of batch type calcination-activation rotary kiln |
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| US4136965A (en) * | 1978-03-31 | 1979-01-30 | Bethlehem Steel Corporation | Mixer block for use in rotary drums |
| CN1187387A (en) * | 1997-01-10 | 1998-07-15 | 中国石油化工总公司 | Process for preparing propene oligomerization solid phosphate catalyst |
| CN1398833A (en) * | 2001-07-20 | 2003-02-26 | 中国石油化工股份有限公司 | Prepn of solid phosphoric acid catalyst for oligomerization of propylene |
| CN102274759A (en) * | 2011-02-23 | 2011-12-14 | 李成生 | Preparation method for propylene oligomerization solid phosphoric acid catalyst |
| CN102764663A (en) * | 2012-07-31 | 2012-11-07 | 彤程化学(上海)有限公司 | Catalyst activation-preabrasion double-function rotary furnace |
-
2012
- 2012-09-28 CN CN201210366357.2A patent/CN102895982B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4136965A (en) * | 1978-03-31 | 1979-01-30 | Bethlehem Steel Corporation | Mixer block for use in rotary drums |
| CN1187387A (en) * | 1997-01-10 | 1998-07-15 | 中国石油化工总公司 | Process for preparing propene oligomerization solid phosphate catalyst |
| CN1398833A (en) * | 2001-07-20 | 2003-02-26 | 中国石油化工股份有限公司 | Prepn of solid phosphoric acid catalyst for oligomerization of propylene |
| CN102274759A (en) * | 2011-02-23 | 2011-12-14 | 李成生 | Preparation method for propylene oligomerization solid phosphoric acid catalyst |
| CN102764663A (en) * | 2012-07-31 | 2012-11-07 | 彤程化学(上海)有限公司 | Catalyst activation-preabrasion double-function rotary furnace |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103743228A (en) * | 2014-01-17 | 2014-04-23 | 中国大唐集团科学技术研究院有限公司 | Industrial rotary kiln |
| CN103743228B (en) * | 2014-01-17 | 2016-02-17 | 中国大唐集团科学技术研究院有限公司 | A kind of industrial rotary kiln |
| CN104971783A (en) * | 2015-06-18 | 2015-10-14 | 江西昌宁化工有限责任公司 | Continuous technology of batch type calcination-activation rotary kiln |
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