CN102895982B - Catalyst roasting-shaping Liang rotation rotary kilns - Google Patents
Catalyst roasting-shaping Liang rotation rotary kilns Download PDFInfo
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Abstract
The present invention relates to two processes of the roasting of solid phosphoric acid catalyst (SPAC) preparation technology a kind of and shaping, the catalyst is applied to the reactions such as low-carbon alkene oligomerisation, propenyl benzene alkylation.Prepared by conventional SPAC, roasting and trimming are carried out respectively, and roasting uses static mode, and material can not fully and thermally equivalent；Shaping uses disintegrating machine, causes low product yield, high broken loss, particle and powder is high and particle inside has " memory " slight crack.Inventor proposes the critical long concept of bar, definitions particles fracture probability function：ζi=k (Li‑Lcri)α, homogeneity bar is fallen from built-in flight top in the turning course of kiln, is hit with bottom, bar length reaches unanimity after fracture, design one shaping Liang rotation rotary kilns of roasting.The SPAC particle lengths and intensity distribution of acquisition are narrow, improve catalytic reaction conversion ratio and oligomer selectivity, reduce its argillization tendency, extension running life.Product particle length of the present invention depends on calcining kiln effective radius (rbs).The present invention can industrial implementation.
Description
Technical field
The invention belongs to solid phosphoric acid catalyst preparation field, and in particular to a kind of catalyst roasting-shaping Liang Yong rotation turns
Kiln, calcining process and trimming prepared by particularly a kind of solid phosphoric acid catalyst.
Background technology
Catalyst for oligomerization has the homogeneous and class of multiphase two.Sulfuric acid, phosphoric homogeneous catalyst, although have reaction rate high and
The advantages of high conversion rate, but product separation is difficult and has the problems such as a large amount of waste liquids need processing, substantially without industry
Device is in application；Multiphase catalyst for oligomerization mainly includes：Zeolite type solid acid catalyst, means of nonzeolitic solid acid catalyst and its
His loaded catalyst.Support type catalyst for oligomerization can substantially be classified as 3 classes：One is with BF3It is sour or super for the load Lewis of representative
Strong acid catalyst for oligomerization；It is another kind of be using nickel, iron as representative carried metal catalyst for oligomerization.Uop Inc. leads in above-mentioned two
Extensive work was made in domain, had applied for many patents；3rd class is the most commonly used solid phosphoric acid catalyst of commercial Application
(SPAC).Uop Inc. and Shanghai Petroleum Chemical Engineering Institute all develop and produced commodity SPAC.
Commodity SPA-1, SPA-2 and SPA-5 of Uop Inc., existing 70 years commercial Application history, have in the world 300 sets with
The SPAC of Uop Inc. is used for a long time in upper commercial plant；SINOPEC Shanghai Petroleum Chemical Engineering Institute undertook country " eight from 1986
Five brainstorm projects "-" oligomerization of propene prepares nonene and synthesis nonyl phenol " starts, and is engaged in propene oligomer catalyst and oligomerization process
Research, develops T-49 solid phosphoric acid catalysts, it (is now Petro China Lanzhou Petrochemicals that 1997, which start in Lanzhou Oil Refinery,
Branch company) commerical test and commercial Application, develop T-99 catalyst again within 1999, further increase the reaction of catalytic oligomerization
Active and anti-argillization ability.
Since being used for alkene oligomerization from the pioneering solid phosphoric acid catalyst of nineteen thirties Uop Inc. of the U.S., so far
The tripolymer and the tetramer for producing it from propylene still use this catalyst.Yet with the easy argillization of solid phosphoric acid catalyst
The disadvantage for causing catalyst life not grown exists all the time, so people are studying the active structure of this catalyst and the new load of exploitation
While body, improvement preparation technology is focused on.
The condition of crystallization steps results in satisfaction in strict control catalyst preparation process in United States Patent (USP) US4946815
Silicon phosphate crystalline content, so as to improve the life-span of SPA catalyst.This was Uop Inc. SPA catalyst patented technology from 1972
Disclosed Section 1 invention later.The SPA catalyst of the invention is that the polyphosphoric acid for making heat at about 170 DEG C (contains P2O582%)
With diatomite mixing, phosphorus acid content therein, with P2O5Meter, mass fraction is optimal more than 80%, and mixture outward appearance is from slightly
Tide arrives what is almost done, but is plastic during extrusion.Make unformed extrusion forming semi-products crystallization after extrusion, pelletizing, from
And obtain finished catalyst.When the key of invention is temperature, steam addition and the crystallization of controlling crystallizing process device therefor
Between.These factor relations siliceous phosphatic type and quantity in finished catalyst.
It is related in China Patent No. CN1960956A in the method for lower polyolefins raw material, by raw material in Oligomerization conditions
It is lower to be contacted with the second catalyst of (a) the first crystalline molecular sieve catalyst and (b) comprising solid phosphoric acid.First and second catalysis
Agent can be included in different reactors or as the different beds in single reactor.I.e. olefin feedstock is in contact solid phosphoric acid
Molecular sieve catalyst is first contacted before catalyst.The stability of this method is higher five times during SPA catalyst than being used alone.Catalyst
It can be got out at the end of operation from reactor.Without what is commonly used in this type of reactor individually using SPA catalyst
Expensive water injection.
A kind of preparation method for propene oligomerization solid phosphoric acid catalyst is proposed in China Patent No. CN1187387A,
Polyphosphoric acids is made at 120-230 DEG C in five phosphorous oxides and phosphoric acid first, phosphoric acid is made at 120-230 DEG C with co-catalyst
Be blended after salt with diatomite, after extruded moulding, the drying process 1-10h at 100-250 DEG C, then with 500-650 DEG C under the conditions of
In Muffle kiln roasting 0.5-24h, catalyst is being obtained using air, the mixing gas disposal of vapor, the preparation method is made
The active height of catalyst, intensity is high, and water resistance is good, the characteristics of rate of wear is small, available in industrial production.
In conventional SPAC preparation process, roasting, two processes of shaping are carried out respectively, are had the following disadvantages：
(1) material is admitted to disintegrating machine after calcining process and carries out broken shaping, and particle produces when broken largely broken
Grain and dust, and there is product abrasion rate height, crush loss greatly, the low problem of yield；
(2) traditional calcining process uses static mode, no matter tunnel cave, or Muffle furnace all exist material to be machined by
The defect that heat is uneven, roasting degree is different, causes product intensity uneven；
(3) product of roasting uses disintegrating machine shaping, and catalyst granules has the slight crack (being commonly called as remembering slight crack) of residual, fortune
The particle of intensity difference, crackled particle are broken in defeated, loading process；The easy argillization of particle during use, causes bed pressure
Power drop rises.
To solve the above problems, inventor devises the double function operation carried out in apparatus for rotating：Roasting-shaping.Obtain
SPAC particle lengths and intensity distribution is narrow, product yield is high, and improve catalytic reaction conversion ratio and oligomer selectivity, drop
Low catalyst argillization tendency, extends running life.The present invention being capable of industrial realization.
The content of the invention
The invention belongs to two processes of the roasting in solid phosphoric acid catalyst (SPAC) preparation field and shaping.The catalyst
Applied to low-carbon alkene oligomerisation reaction, propenyl benzene alkylated reaction.Prepared by solid phosphoric acid catalyst, be closely related by 5
Process：Polyphosphate prepares (reaction), poly phosphorus boric acid complex salt and prepares (kneading), continues the boric acid complex salt system of poly phosphorus
Standby (homogenizing), shaping and dry, acquisition catalyst firing precursor.Traditional subsequent handling is：Roasting, shaping, activation and sieve
Point, obtain finished product SPAC.Roasting is that unformed silicophosphate is converted into crystal type salt；Shaping is the catalyst for making length different
The particle reached unanimity as length.
Present invention aims at the difunctional process being carried out continuously in a kind of solid phosphoric acid catalyst preparation technology of offer：Roasting
Burning and particle shaping, homogeneous, diameter 3mm~7mm urge is obtained by reaction, kneading, homogenizing, shaping, dry 5 processes
Agent precursor, then passes through roasting and particle shaping process, activation and preliminary abrasion process obtain finished product.
Another object of the present invention is to provide roasting, two processes of shaping to realize using difunctional equipment：It is difunctional
The rotation rotary kiln of roasting-shaping two, the process for realizing two not same-actions in same equipment.
The wherein described use rotation rotary kiln internal diameter of roasting-shaping two, according to catalyst granules length requirement, depending on structure
Parameter alpha (=f (rbs)), rbsIt is calcining kiln cylinder internal diameter, the difunctional roasting determined using half experiment and semi-analytic method-whole
Shape kiln internal diameter rbs=φ 1.8m~2.5m.
Described roasting-shaping Liang Yong rotation rotary kiln be the difunctional roasting of flight formula-shaping Liang rotation rotary kilns, cylinder by
Preheating, 3 region compositions of roasting and cooling, it is desirable to which 120 ° of flights are set in total length >=20m, cylinder, circumferentially 60 ° of dislocation cloth
Put, a length of 0.3~1.2m of every piece of flight, flight width is (1/10~1/6) .rbs。
Described roasting-shaping Liang Yong rotation rotary kilns are along roasting-shaping Liang Yong rotation rotary kiln length, at the adherent place of inner barrel
3~10 temperature measuring points are set, preheating section, furnace zone and cooling section temperature are determined respectively, wireless temperature measurement component is used.
In the present invention, inventor proposes：" the critical bar of the contour whereabouts fracture of same diameter physical property circle strip-shaped materials of the same race is long
Concept ", defines above-mentioned bar fracture probability function：ζi=k (Li-Lcri)α。
In the difunctional revolution calcining kiln of the present invention, while material experience roasting, as cylinder rotates, diameter is identical
Cylinder strip precursor be fixed on the knuckle flight of cylinder inboard wall and take up and lifted therewith from cylinder bottom, and gradually from flight
Front end slides.From cylinder cross section, the catalyst precarsor of landing is fallen as " curtain of rain ", and whereabouts precursor is with being located at cylinder
Bottom impacts and fracture, the particle length after fractureing is unrelated with precursor the original length, and meet inventor proposition fracture
Probability：Longer material is easier to be disconnected, that is, the probability that fractures is big；Short material is not easy to break, and probability is small；Bar is a length of, and some is critical
The particle of value, fall to be broken under such condition, and probability is zero.Make to enter the enough kilns of barrel lenght, the material of stove, nothing
By taking up, falling by how many times, the product length of acquisition reaches unanimity.Fracture probability is defined：
ζi=k (Li-Lcri)α (1)
In formula：ζi：Bar i fracture probability, %；
α：The breaking strength index relevant with mechanical structure, α=f (r), r is the effective radius of cylinder；
k：The parameter relevant with bar nature, k=f (RP/W)；RP/WIt is phosphorus, the water ratio of material；
Li：Bar i length；
Subscript i=1,2,3 ..., n, granule number n are the big quantity of correspondence probability；
Lcri：The critical length of bar, is under the broken condition, falls, collides the bar length being no longer broken；
According to above-mentioned concept and fracture probability：In the turning course of kiln, particle is fallen from flight top, is hit with bottom
Hit, cause the bar length of fracture to reach unanimity.Inventor devises the double function operation carried out in apparatus for rotating：Roasting-
Shaping.The SPAC particle lengths and intensity distribution of acquisition are narrow, product yield is high, and improve catalytic reaction conversion ratio and oligomer
Selectivity, reduces catalyst argillization tendency, extends running life.Product particle length of the present invention depends on calcining kiln effectively half
Footpath rbs.The present invention being capable of industrial realization.
The present invention improves SPAC running lives and alkene turns while SPAC product yields and running effect is improved
Rate.The present invention can be with industrial implementation.
Brief description of the drawings
Fig. 1 is material in calcining kiln cross-sectional view of the present invention.It can be seen that as kiln rotates, flight is by precursor granules
Take up to come from bottom, particle slides from flight top, drops to bottom of cylinder, collides and be broken with the particle of bottom.
Embodiment
Catalyst firing precursor is obtained in solid phosphoric acid catalyst (SPAC) preparation process has 5 works being closely related
Sequence：Polyphosphate prepares (reaction), poly phosphorus boric acid complex salt and prepares (kneading), continues the preparation of polyphosphoric acids boric acid complex salt
(homogenizing), it is molded and dries.Traditional subsequent handling is：Roasting, shaping, activation and screening, obtain finished product SPAC.
Catalyst firing precursor comes subsequent handling with " memory " of 5 process operations above.First in swinging
Flight roasting-shaping kiln, is calcined, and by catalyst precarsor be broken into as defined in bar it is long.
The SPAC preparing raw materials that the present invention is used are shown in Table 1, and product quality and the comparative example quality of acquisition are shown in Table 2.For this
The SPAC firing precursors of invention come from drying process, major traits：Diameter 5mm~6mm；Length, is 10mm~80mm's
Uniform cylindrical bar.
The embodiment raw material physicochemical property of table 1
Catalyst oligomerisation reaction activity rating is carried out on the single tube fixed bed reactors experimental rig of laboratory, reactor dress
Carry the SPAC particles for being broken into 2mm sizes, volume 10mL；The condition of embodiment and contrast test listed by table 2：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, reaction
200 DEG C of temperature, reaction pressure 4.8MPa.Test raw material gas and tails assay are carried out online using 102 gas-chromatographies, and device is stable
20h is operated, reactor outlet tails assay obtains the hydro carbons composition represented with mole fraction, and the mixed butene for calculating the reaction turns
Rate, is used as oligomerisation reaction activity value.Butene conversion calculating formula：
x∑C4=1- [(nC4H8·n0C4H10)/(nC4H10·n0C4H8)]×100 (3)
In formula：x∑C4For mixed butene conversion ratio, %；n0C4H8, n0C4H10Butylene and butane is mole dense respectively in raw material
Degree, nC4H8, nC4H10The molar concentration of butylene and butane respectively in tail gas.
Embodiment
The present invention industrial flight formula roasting-dual-purpose rotary kiln of shaping (kiln cylinder body length 29m, it is interior through rbs=φ 2.0m)
Implement.Kiln cylinder body tilts 2.5%, and cylinder inboard wall has 120 ° of knuckle flights, per block length 0.4m, and width is (1/8) .rbs；Along circle
24 ° of settings of week, every group 15 pieces；Adjacent flight staggers 12 °.The calcining kiln used is external-heat, and fuel is bituminous coal；By preheating section,
Furnace zone, cooling section composition；Kiln inwall sets temperature element, determines each section of temperature.
The precursor sent with conveyer belt from drying process is continuously added to kiln body from roasting kiln hood, is calcined kiln cylinder body rotational speed
For 0.25r/min, the roast area temperature control of calcining kiln is in 590 DEG C, residence time 80min；Together with preheating, cooling, material exists
Total residence time is 2.5h in calcining kiln.The catalyst granules for leaving calcining kiln falls into circular reciprocating sieve from kiln tail, and compass screen surface is 50
Mesh standard sieve, removes fine particle and the later product of roasting of powder enters the storage bin of activation procedure,
Fig. 1 is material in calcining kiln cross-sectional view of the present invention.It can be seen that as kiln, stove rotate, flight is by precursor
Particle is taken up from bottom, and particle slides from flight top, drops to bottom of cylinder, collides and be broken with the particle of bottom.
Implement experiment to be carried out continuously in commercial scale plant, take 24h service datas therein and finished product as embodiment sample
This.Operating condition：Calcining kiln feeds intake from drying process, inventory：300kg/h, 150 DEG C of temperature, continuously enters kiln hood；Data
During collection, preheating section temperature rises to 577 DEG C, 587 DEG C of furnace zone mean temperature from 150 DEG C, cooling section temperature is by 585 DEG C
170 DEG C are dropped to, enters activation procedure storage bin after rotary strainer separates particle and powder from product after kiln.24h roastings are total to throw
Expect that 24h collections obtain 157kg crushed particles and powder under 7200kg, rotary strainer, average 4.13kg/h, roasting-trimming yield
97.8%.
The outturn sample that above-mentioned experiment is obtained enters activation procedure, and activation products obtain finished product and urged through 50 mesh rotary strainers, upper strata
Agent, keep sample 100g per hour, and 24h obtains sample 2400g, therefrom sampling analysis, test, the product quality analysis result of acquisition
It is shown in Table 2.Control sample is the production piece that Uop Inc. is supplied to certain domestic petro-chemical corporation, and test, evaluation are entered by laboratory of the present invention
OK, as a result list file names with, for reference.
The embodiment SPAC of table 2 and certain Products mass ratio compared with
[1] comparative sample is UOP SPA-2, industrial products, by this researcher practical measurement.
Claims (1)
1. the difunctional process being carried out continuously in solid phosphoric acid catalyst preparation technology：Roasting and particle shaping, by reacting, pinching
Close, homogenizing, shaping, dry 5 processes and obtain homogeneous, diameter 3mm~7mm catalyst precarsors, then pass through roasting and
Particle shaping process, activation and preliminary abrasion process obtain finished product, it is characterised in that described roasting, two processes of particle shaping are adopted
Realized with difunctional equipment：The difunctional rotation rotary kiln of roasting-shaping two, two not same-actions are realized in same equipment
Process, the internal diameter of roasting-shaping Liang Yong rotation rotary kilns, according to catalyst granules length requirement, depending on structural parameters α (=f
(rbs)), rbsIt is calcining kiln cylinder internal diameter, the difunctional roasting-shaping Liang rotation determined using half experiment and semi-analytic method
Rotary kiln internal diameter rbs=Φ 1.8m~2.5m；
Described roasting-shaping Liang is the difunctional roasting of flight formula-shaping Liang rotation rotary kilns Yong rotation rotary kiln, and cylinder is by pre-
Heat, 3 region compositions of roasting and cooling, it is desirable to which 120 ° of flights are set in total length >=20m, cylinder, circumferentially 60 ° of dislocation arrangements,
A length of 0.3~the 1.2m of every piece of flight, flight width is (1/10~1/6) rbs, along roasting-shaping Liang Yong rotation rotary kiln length,
The adherent place of inner barrel sets 3~10 temperature measuring points, and preheating section, furnace zone and cooling section temperature are determined respectively, uses wireless survey
Warm component.
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| 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 |
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 |
-
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 |
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