CN1078494C

CN1078494C - Preparation of solid phosphoric acid catalyst

Info

Publication number: CN1078494C
Application number: CN98100103A
Authority: CN
Inventors: 刘希尧; 陈振强; 栗同林; 靳芝晔; 张天巧; 马飞; 郭仲福; 赵天宇; 周洪; 梁凤金
Original assignee: Beijing Research Institute of Beijing Yanshan Petrochemical Corp
Current assignee: Beijing Research Institute of Beijing Yanshan Petrochemical Corp
Priority date: 1998-01-06
Filing date: 1998-01-06
Publication date: 2002-01-30
Anticipated expiration: 2018-01-06
Also published as: CN1222407A

Abstract

The present invention relates to a method for preparing a solid phosphoric acid catalyst. Auxiliary agent talcum powder is added to polyphosphoric acids and substrate containing SiO2 (kieselguhr is preferable), the mixture is stirred at the speed of 10 to 40 rpm at the temperature of 130 to 210 DEGC and is kneaded until the mixture is solidified and a sanded phenomenon occurs, and the mixture is extruded and formed and is roasted at the temperature of 300 to 375 DEGC. The total pore volume of the solid phosphoric acid catalyst is from 0.12 to 0.25 ml/g, and the pore volume of the solid phosphoric acid catalyst which is larger than 1 um is less than 0.04 ml/g.

Description

Preparation of solid phosphoric acid catalyst

The present invention relates to a kind of manufacture method and application thereof of solid phosphoric acid catalyst.

Solid phosphoric acid catalyst is usually used in the alkylation reaction of alkylating agents such as benzene class aromatic hydrocarbons and alkene, also can be used for reactions such as low-carbon alkene oligomerisation and esterification.Its belongs to profit and carries acid type solid acid catalyst, by phosphorous acid with contain SiO ₂The compound roasting of porous matrix form.US256852 discloses its basic process, is base stock with polyphosphoric acids and kaolin or silica.The effective pore volume of US 3044964 report restrictions is to improving the significance of this class catalyst stability, and disclosing control is 0.07～0.20ml/g greater than 900nm hole (directly) pore volume directly, accounts for the technology of preparing of total pore volume≤17.5%.1056828 of US 4912279 and CN further propose the control hole structure to improve the technology of preparing of catalyst strength and reaction stability, it is characterized in that the hole of aperture 〉=1000nm should be less than 17.5% of total pore volume, and the catalyst total pore volume is less than 0.28ml/g.US 3112350,3673111, and 3801704 and 4521638 propose the intensity of solid phosphoric acid catalyst, and the reaction life-span is subjected to the very big influence of sintering temperature, also special roasting mode and the relation that improves crystallization phosphoric acid silicon of proposing of US5059737 and CN 1058729.Take a broad view of the technology of existing solid phosphoric acid catalyst, be summarised as following 3 contents: (1) mainly is polyphosphoric acids and siliceous inorganic oxide with a kind of phosphoric acid, mainly is that diatomite is raw material; (2) at 10～230 ℃, best 90～180 ℃ of mixed materials acid becomes moist shape agglomerate with soil, and extrusion molding; (3) extrudate 240～500 ℃ under abundant water vapour environment roasting become solid phosphoric acid catalyst.But, there is not fully to disclose the technology key that to hold in acid and the native raw material mixed process so far, therefore adopt the phosphoric acid catalyst of prior art preparation, acid during often because of extrusion molding-earth mixtures agglomerate ease acid, be difficult for extruding, the calcined catalyst particle after extruding is the bonding and moisture absorption easily, causes the acidity of catalyst lower, reactivity is low and unstable, and the easy argillization of intensity difference.

In view of this, it is that a physical and chemical process that influences the solid phosphoric acid catalyst person's character is started with that the present invention mixes from understanding (poly phosphorus) acid-(diatom) soil, purpose is to overcome above-mentioned technical deficiency, and a kind of method for preparing control premium properties solid phosphoric acid catalyst is provided.

(poly phosphorus) acid and (diatom) soil mix at a certain temperature, and the infiltration of acid to soil promptly takes place, and liquid-solid adsorption phenomena occurs.Create appropraite condition and impel moisture content and volatile component desorption in the native hole, will help acid diffusion and absorption in the hole of soil.The mixed material of suitable sour soil ratio is when 180 ℃ of left and right sides, and the sour institute filling that most of hole of soil is adsorbed, and the particle outer surface still can adhere to a small amount of acid solution is so cause acid one soil of rapid caking to solidify phenomenon (Solidification).If stop heating this moment, the agglomerate that acid-soil mixes is difficult for broken, not only extrusion molding difficulty, and the sour phenomenon of ease takes place.So in roasting process subsequently, because acid can not solid phase reaction take place fully with soil, cause active phase phosphoric acid silicon and pyrophosphoric acid silicon degree of crystallinity not high, the surface ease is stayed phosphoric acid then to decompose and is generated amorphous P ₂O ₅, influence catalyst strength, be easy to argillization.The present invention finds, when the sour soil mixture solidified follow-up of continuing rising to 190～210 ℃, the acid solution that remains in the diatomite particle surface can further be adsorbed by soil, fully discharge chemisorbed heat simultaneously, so cause that the sand shape of acid-earth mixtures cured mass is cracked, sandization (Sand-breaking) phenomenon promptly take place.Only reach the acid of just fully having maintained the achievements of one's predecessors of this state and mix with the acid-soil of soil, thus the appearance sour phenomenon of escaping when not only having avoided extruding, and guaranteed that roasting makes the active phase of high-crystallinity phosphoric acid silicon.

The present invention also finds, realize the good sandization of mixed acid-soil, require (1) acid suitable with the charge ratio of soil, be generally 2.5/1 weight ratio～4/1 weight ratio, (2) acid mixes with soil, fully contact mutually, must give heating polyphosphoric acids to 135～145 ℃ scope, add diatomite and auxiliary agent, wherein the addition of auxiliary agent accounts for the 1-5% of inventory, auxiliary agent preferably talc powder, and under stirring, 10～40rpm continues to be warmed up to curing, (3) 180 ℃ of follow-up continuing of curing are warmed up to 190～210 ℃, preferred 190～200 ℃, realize good sandization.The mixed material of good sandization, after the moulding can need not outside under the water filling vapour condition roasting make and have well-crystallized mutually and the solid phosphoric acid catalyst of pore structure.

According to above-mentioned feature, solid phosphoric acid catalyst method for making of the present invention is as follows:

Press the sour soil charge ratio, best 3/1 weight ratio, take by weighing polyphosphoric acids and diatomite respectively, in the still that feeds intake, give earlier heated phosphoric to 135～145 ℃, best 140～145 ℃, control mixing speed 10～40rpm, best 20～30rpm adds down a certain amount of auxiliary agent and diatomite, be warmed up in 8～10 minutes 180 ℃ mixing cured, continue to be warming up to sandization and end, after stopping heating and stirring the discharging extrusion modling, in 250～450 ℃, best 300～375 ℃, roasting promptly got the solid phosphoric acid catalyst of the present invention's preparation in 1～2 hour under steam condition, its Main physical proterties is: φ=6 (± 0.5) * 6 (± 2) mm cylindrical pellet, white, the broken intensity 3.5Mpa/cm of axial compression resistance, bulk density 0.9 ± 0.1g/ml, total pore volume 0.12～0.25ml/g, greater than 1 micron pore volume less than 0.04ml/g.

Solid phosphoric acid catalyst of the present invention is mainly used the aromatic hydrocarbons alkylation reaction, also can be used for olefin(e) oligomerization, is specially adapted to the alkylation reaction of benzene or toluene and propylene.

In order to further specify solid phosphoric acid catalyst preparation method and its usage of the present invention, provide following example now.

Embodiment 1～4

In one 30 liters stainless steel stirred tank, add 21 kilograms of 80%P ₂O ₅Polyphosphoric acids, be preheating to each temperature shown in table 1 embodiment 1～4, feed intake (weight) than 3/1 adding 7 kilograms of diatomite (Faku County's product) by acid/soil, add the auxiliary agent talcum powder, under same mixing speed and programming rate, mix and pinch, roasting obtains the different solid phosphoric acid catalyst of performance under identical optimization roasting condition then, the result of table 1 show initial temperature that diatomite adds phosphoric acid directly influence mix the sand state of pinching, after just then determine the finished catalyst performance.Table 1

Poly 130 140 145 150 phosphoric acid gave hot temperature when embodiment 1234 began to add diatomite, ℃ mix and to pinch 175 ℃ of curing of state, 180 ℃ of curing, 180 ℃ of curing, 180 ℃ very fast solid

190～195 ℃ of groupizations of 190～195 ℃ of groups of 190～195 ℃ of groups, caking is uneven

It is not clear that piece is difficult for the clear even sandization of the clear sandization of sand piece sandization

Show solid phosphoric acid catalyst performance free acid, P ₂O ₅% 12.0 18.8 18.9 11.5 crush strengths, MPa/cm ²2.1 3.7 3.8 1.4

Embodiment 5～7

With example 1 polyphosphoric acids is preheating to 140 ℃, feed intake (weight) than 3/1 adding diatomite by acid/soil, add the auxiliary agent talcum powder, control mixing speed 25rpm, obtain the mixed material that different blended is pinched effect by table 2 and accompanying drawing 1～3 different programming rates, show the different states of extruding during extrusion molding, roasting under identical optimization roasting condition then obtains the different solid phosphoric acid catalyst of performance.

Table 2

The embodiment 567 mixed mixed states of pinching of programming rate curve map 1 Fig. 2 Fig. 3 of pinching solidify good, sour soil mixes equal prolongation hardening time, solidify rapidly, do not go out

Even, the existing sandization of sandization does not appear in 190～195 ℃ of sandization, solidifies group

Go up the single screw rod of the irregular extrusion molding situation of sour soil for clear and extrude smoothly, squeeze single twin-screw and be difficult for extruding, squeeze list and twin-screw and extrude

Go out load current and go out load current greater than 10A less than 5A, difficulty is extruded load

Ease sour electric current in extrudate surface is greater than 10A solid phosphoric acid catalyst performance free acid, P ₂O ₅% 20.9 8.7 7.7 resistance to compression rate intensity, MPa/cm ²3.9 2.3 2.1 embodiment 8～14

Embodiment 5 sandization are material clearly, by the solid phosphoric acid catalyst that table 3 makes under different roasting conditions, illustrates 350～375 ℃ and under steam condition, can both obtain the catalyst of premium properties.(1)

Table 3

Embodiment 89 10 11 12 13 14 sintering temperatures ℃ 375 365 365 365 350 330 380 steam controlled conditions from steam water filling vaporization from steam tail gas air draft retaining from steam from steam from steam

4L/4h is semiclosed, from

The positive pyrophosphoric acid silicon of steam solid phosphoric acid catalyst performance degree of crystallinity, % 32.3 40.1 40.5 40.8 40.3 31.3 29.8 presses the mercury total pore volume, ml/L 0.144 0.221 0.152 0.156 0.183 0.253 0.125 is greater than the 1um pore volume, ml/L 0.025 0.039 0.029 0.033 0.035 0.064 0.021 free acid, P ₂O ₅% 18.2 20.7 21.8 21.3 20.9 14.8 7.35 hydrocarbonylation activity, (1)

Benzene conversion ratio % 11.04 12.20 12.65 12.52 12.37 10.22 9.41

Propylene conversion % 92.3 96.4 96.7 96.42 96.52 95.31 75.20 (1) alkylation reaction conditions:

T=215 ℃, P=3.5MPa, benzene/propylene (mol ratio)=7.5/1, propane/propylene (mol ratio)=2/1, benzene feeding liquid hourly space velocity 1hr ^-1, stable reaction was taken a sample through chromatography after 8 hours.

Embodiment 15～19

Mix and to pinch that to present good sand state relevant with the adding auxiliary agent.Embodiment 15～19th, and the acid that feeds intake/soil is than 3/1, and polyphosphoric acids is preheating to 140 ℃ by table 4 adding diatomite and different auxiliary agents, and the identical resulting different solid phosphoric acid catalysts of other condition subsequent can illustrate the effect of auxiliary agent.

Table 4 embodiment 15 16 17 18 19 auxiliary agent boehmite calcium oxide powder talcum powder talcum powders add addition, % 2214 mix the situation of pinching with squeeze mix pinch when long solid mix to pinch sand occurs and mix to pinch to occur mixing pinching and sand occurs and mix to pinch and solidify moulding situationization and sandization, extruding but sand removalization not really, crowdedization, extrude the length that postpones, sand

Difficulty is clear, and it is unclear to be extruded into out smooth profitization,

Type is extruded difficult solid phosphoric acid catalyst performance free acid, P ₂O ₅% 11.2 18.6 20.3 21.0 16.4

Claims

1 one kinds of methods that are used to make solid phosphoric acid catalyst, after it is characterized in that the raw material polyphosphoric acids is heated to 135～145 ℃, add silicon bath soil and auxiliary agent down in stirring, wherein polyphosphoric acids and diatomaceous weight ratio are 2.5/1-4/1, and auxiliary agent is a talcum powder, and its addition accounts for the 1-5% of inventory, and continue to be warming up to 180 ℃ and mix down to pinch to material and solidify, solidify and follow-uply continuous be warmed up to 190-210 ℃ sandization, sandization is after the extrusion molding roasting is made, and wherein roasting is to carry out under 250-450 ℃ of temperature.

2 methods according to the described manufacturing solid phosphoric acid catalyst of claim 1 is characterized in that stir speed (S.S.) is 10-40rpm, and the sand temperature range is 190-200 ℃.

3 methods according to the described manufacturing solid phosphoric acid catalyst of claim 2 is characterized in that stir speed (S.S.) is 20-30rpm.

4 methods according to the described manufacturing solid phosphoric acid catalyst of claim 1 is characterized in that sintering temperature is 300-375 ℃.

5 purposes of solid phosphoric acid catalyst in aromatic hydrocarbons hydrocarbonylation or olefin oligomerization of making according to the described method of claim 1-5.