CN1008074B - Method for steam treatment of diatomite carrier - Google Patents
Method for steam treatment of diatomite carrierInfo
- Publication number
- CN1008074B CN1008074B CN 88105060 CN88105060A CN1008074B CN 1008074 B CN1008074 B CN 1008074B CN 88105060 CN88105060 CN 88105060 CN 88105060 A CN88105060 A CN 88105060A CN 1008074 B CN1008074 B CN 1008074B
- Authority
- CN
- China
- Prior art keywords
- carrier
- pressure
- diatomite
- steam treatment
- carriers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a method for treating steam of diatomite carriers, which comprises the following steps: soaking carriers by adopting phosphoric acid with concentration between 40 and 75%, treating the carriers by using steam and air, or mixed gas of steam and nitrogen with 20 to 230 hr<-1> of the airspeed and 0.3 to 0.6 of the water air ratio under 4 to 24 kg/cm<2> of the pressure, and then carrying out other procedures with 250 to 350 DEG C of the treating temperature and 3 to 6 hours of the retention time. Olefin hydration, hydrogenation and oxidation catalyst carriers with high mechanical strength, large pore volume and suitable hole diameter can be prepared by using the method, and the method can also be used for manufacturing insulation devices, thermal insulation devices and filter devices.
Description
The present invention relates to a kind of TREATING METHOD FOR DIATOMACEOUS SUPPORT, it comprises with certain density phosphate impregnation carrier, then under predetermined pressure, handles steps such as carrier once more with the gas of a certain specific water partial pressure, belongs to chemical catalyst carrier manufacturing technology.
Carry phosphoric acid as the existing many decades history of olefin hydration industrial catalyst with the diatomite profit in the chemical industry, it is low to expose the carrier mechanical strength in actual the use, and therefore shortcomings such as poor stability have reduced activity of such catalysts.In order to overcome above-mentioned shortcoming, documents and materials have been introduced with bonding diatomaceous high-temperature roasting method of clay and alkaline process and have been prepared carrier.But, adopt the diatomite support intensity of this method preparation still lower, and pore structure is damaged to a certain extent; The another kind that document is recommended with the moulding of silica gel mixing diatomite after, through 1050 ℃ of high-temperature roastings, prepared high strength carrier, also because under high-temperature condition, the microcellular structure of carrier is damaged, and unfavorable factor such as total pore volume minimizing, and is difficult to obtain high-quality catalyst carrier.At USP2, introduced phosphate impregnation carrier in 960,477 with 75～98% concentration, then under normal pressure with the mixed carrier gas processing of water vapour and nitrogen, and at 50kg/cm
2Under the above pressure, with the method for the nitrogen static treatment carrier that contains certain water partial pressure.When adopting this patented method to prepare carrier, though still also exist the pore volume of preparation under the normal pressure bigger, mechanical strength is on the low side; Though the carrier mechanical strength that the mesohigh static treatment is obtained is higher, deficiency such as less than normal and hole smoothness difference of pore volume.
At the deficiency of above-mentioned several method, the present invention proposes a kind of mechanical strength height that obtains, the preparation method of the diatomite support that the big and aperture of pore volume is suitable.
The inventive method is based on, in the diatomite support process of steam treatment impregnation of phosphoric acid, because the catalytic action of phosphoric acid, the one-step polymerization of going forward side by side is dissolved in the dehydration silicon gel generation depolymerization on diatom test surface, forming one deck silica gel thin film covers on the diatom test skeleton, diatom test is interconnected by the Si-O-Si bridge in some position, in this process, also exist the gas-migration effect of product, thereby can change the reaction mechanism of the aperture structure of carrier, and carrier dissolving and generate gel when washing according to normal pressure concentrated acid dynamic process sample, the fact that low pressure dynamic process sample specific area increases and average pore size reduces puts forward.
The technical characterictic of the inventive method is in particular in: adopt the phosphate impregnation carrier of 40～75% concentration, then at 4～24kg/cm
2Under the pressure with 20～230hr
-1Air speed, WGR are 0.3～0.6 water vapour and air, the perhaps mixed carrier gas processing of water vapour and nitrogen, 250～350 ℃ of treatment temperatures, 3～6 hours retention times.
The technical characterictic of the inventive method can also further be expressed as, and be to obtain bigger specific area carrier, and processing pressure can be taked the mode that increases progressively in handling overall process, perhaps take in different phase, limits the way of different pressures value.
Because the inventive method adopts dynamic process, carrier pickling concentration is lower, mist both can be water vapour and nitrogen, can be again water vapour and air, the preparation cost of gained carrier is lower than other general method, and the rerum natura overall target of carrier, is higher than the carrier that other method obtains, and treated carrier soaks the catalyst that the catalytic activity of the catalyst for hydration of olefines that phosphoric acid makes also is better than other method preparation, but also possesses good anti-water-wet ability.(seeing Table 1～4)
Below in conjunction with specific embodiment, further narrate technical characterictic of the present invention.
Embodiment 1:
(diatomite support of φ 6 * 4mm) flooded 1 hour with the phosphoric acid solution of 72% concentration, dripped acid 1 hour, packed into after the drying to press in the thermal reactor and handled the gross pressure 24kg/cm of system with sheet after the roasting
2; Nitrogen air speed 200hr
-1; WGR 0.49; Under 300 ± 5 ℃ of conditions, kept 3 hours, draw off the back, make carrier after the drying with the distilled water washing.
This carrier average radial crushing strength is the 3.63kg/ grain; Pore volume 0.840ml/g; Average pore size 2.50 * 10
3 
Embodiment 2
With the phosphate impregnation carrier of 75% concentration, in the temperature identical, under pressure and the air speed, to handle 3 hours with embodiment 1, WGR is 0.42.The carrier that makes radially crushing strength is the 5.48kg/ grain, and axially crushing strength is 151.6kg/cm
2; Pore volume 0.850ml/g; Average pore size 1.60 * 10
3
Embodiment 3
Carrier crushing strength 1.39kg/ grain radially after the roasting; Pore volume 0.704ml/g; Specific area 16.9M
2/ g; Average pore size 0.83 * 10
3A.Phosphate impregnation with 75% concentration.At pressure is 4kg/cm
2System in handle.300 ℃ of temperature, WGR 0.50, nitrogen air speed 200hr
-1, 3 hours retention times, prepared carrier radially crushing strength is the 2.22Kg/ grain; Pore volume 0.800ml/g; Specific area 47.6M
2/ g; Average pore size 0.34 * 10
3 
Embodiment 4
Radially crushing strength is the 0.97kg/ grain, pore volume 0.799ml/g, specific area 15.1M
2/ g, average pore size 1.06 * 10
3The diatomite support of A is with the phosphate impregnation of 75% concentration.Under the condition identical, handle, but carrier gas is an air with embodiment 1.The carrier of final preparation radially crushing strength is the 3.86kg/ grain; Pore volume 0.803ml/g; Specific area 6.67M
2/ g; Average pore size 2.41 * 10
3
Embodiment 5:
With embodiment 4 identical carrier,, handle under the same conditions with 55% phosphorus concentration acid dip.The carrier that is obtained radially crushing strength is the 4.25kg/ grain; Pore volume is 0.786ml/g; Specific area 6.02M
2/ g; Average pore size 2.61 * 10
3
Embodiment 6:
Adopt embodiment 4 identical carrier, 50hr
-1Air speed, other treatment conditions are identical with embodiment 4, and the gained carrier aperture increases, pore volume 0.801mg/g, average pore size 3.21 * 10
3(
), carrier radially crushing strength reduces.
Press the prepared carrier of the foregoing description, impregnation of phosphoric acid promptly can be made into catalyst for hydration of olefines.
Utilize the inventive method except can obtaining high-quality catalyst for hydration of olefines carrier, also because the gained carrier has bigger average pore size and very low impurity content, especially Fe
2O
3The good characteristic that content is very low, and the inertia to reacting make this method become the means of preparation hydrogenation of olefins and oxidation catalyst carrier simultaneously.
In the inventive method, because diatomite support is by phosphate impregnation, most Fe wherein
2O
3Deng impurity with the soluble phosphoric acid salt form by flush away, products therefrom intensity again than higher, obviously can be used for making the insulation device.Because the high porosity of the diatomite support of handling hangs down the conduction characteristic, make and can utilize the inventive method to prepare heat insulation device that the inventive method can also be diffused into the preparation high voidage again, high strength, but in the production of the filter element of aperture appropriate change.
Fe
2O
3The good characteristic that content is very low, and the inertia to reacting make this method become the means of preparation hydrogenation of olefins and oxidation catalyst carrier simultaneously.
In the inventive method, because diatomite support is by phosphate impregnation, most of Fe wherein
2O
3Deng impurity with the soluble phosphoric acid salt form by flush away, products therefrom intensity again than higher, obviously can be used for making the insulation device.Because the high porosity of the diatomite support of handling hangs down the conduction characteristic, make and can utilize the inventive method to prepare heat insulation device that the inventive method can also be diffused into the preparation high voidage again, high strength, but in the production of the filter element of aperture appropriate change.
The carrier rerum natura of table 1, different process preparation relatively
Numbering technology granularity radial strength pore volume average pore size
(mm) (kg/ grain) (ml/g) (
）
1 clay adds diatomite high temperature method D5.5 1.26 0.790 2.70 * 103
2 diatomite alkaline process φ 6 * 4 1.71 0.770 12 * 103
3 83% phosphoric acid, normal pressure processing D5.5 0.93 0.860-
4 72% phosphatase 24 2kg/cm
2φ 6 * 4 3.91 0.750 3.70 * 10
3
5 55% phosphoric acid 24kg/cm
2Dynamic φ 6 * 4 4.25 0.786 2.61 * 10
3
6 75% phosphoric acid 24kg/cm
2Dynamic φ 6 * 4 5.48 0.850 1.60 * 10
3
Table 2, propylene hydration catalyst performance are relatively
Sample list conversion ratio gets pure amount selectivity and loses sour rate sample time
Journey (%) (g/l, hr) is (kg/M (%)
3, hr) (hrs)
West Germany veba 2.60 87.1 91.0 0.87 * 14
10
-3
Nanjing silica gel 4.30 138.8 99.0 0.75 * 4
10
-3
High-temperature roasting 2.71 92.6 94.5 0.68 6
Method * 10
-3
Alkaline process 3.18 107.3 96.7 20.4 * 8
10
-3
This method 4
#5.32 173.2 96.6 0.38 * 40
10
-3
Table 3, ethylene hydration catalyst performance are relatively
Sample phosphorus acid content conversion ratio gets pure amount and loses sour rate running time
（%） （%） （g/l、hr） （kg/M
3、hr） （ms）
West Germany veba 35.80 3.90 82.36 5.11 * 10
-3188
This institute treatment samples 41.66 4.75 104.89 3.63 * 10
-3188
Nanjing silica gel 37.52 3.81 77.56 16.30 * 10
-343
This institute treatment samples 45.10 4.47 100.13 3.60 * 10
-342
Table 4, catalyst water-wet strength ratio are
Sample carrier pore volume dry tenacity water-wet strength descending water soaks the time
(ml/g) (kg/ grain) (kg/ grain) (%) (minute)
West Germany veba 0.70 3.16 2.39 24.4 100
Nanjing silica gel 0.79 4.56 4.20 7.9 100
This institute treatment samples 0.85 4.76 4.63 2.7 100
Air-treatment sample 0.80 3.75 3.51 6.4 100
Alkaline process sample 0.77 2.27 1.68 26.0 100
Jinzhou superimposed-4.46 2.97 33.4 60
Claims (3)
1, a kind of steam treatment process of diatomite support, comprise with certain density phosphate impregnation carrier, then under predetermined pressure, with a certain specific water partial pressure gas, in selected treatment temperature, keep the regular hour to handle steps such as carrier once more, it is characterized in that the carrier after the impregnation of phosphoric acid, at 4～24kg/cm
2Under the pressure, with 20～230hr
-1Air speed, WGR are 0.3～0.6 water vapour and air gas mixture processing carrier;
2, the steam treatment process of diatomite support according to claim 1, pressure increases progressively in overall process when it is characterized by processing;
3, according to the steam treatment process of claim 1,2 described diatomite supports, it is characterized by pressure when handling, take stage increasing progressively; In promptly first hour 4kg/cm
2, 16kg/cm in second hour
2, remaining time pressure is 24kg/cm
2
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105060 CN1008074B (en) | 1988-04-29 | 1988-04-29 | Method for steam treatment of diatomite carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105060 CN1008074B (en) | 1988-04-29 | 1988-04-29 | Method for steam treatment of diatomite carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1030365A CN1030365A (en) | 1989-01-18 |
| CN1008074B true CN1008074B (en) | 1990-05-23 |
Family
ID=4833291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88105060 Expired CN1008074B (en) | 1988-04-29 | 1988-04-29 | Method for steam treatment of diatomite carrier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1008074B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1078494C (en) * | 1998-01-06 | 2002-01-30 | 北京燕山石油化工公司研究院 | Preparation of solid phosphoric acid catalyst |
| CN102335587B (en) * | 2010-07-21 | 2015-12-16 | 姜玉芝 | The preparation method of diatomite adsorbant and product |
| CN101920214A (en) * | 2010-07-27 | 2010-12-22 | 中国科学院等离子体物理研究所 | Method for modifying kieselguhr sulfuric acid catalyst carrier |
| CN103894143B (en) * | 2014-03-18 | 2016-04-20 | 苏州宇希新材料科技有限公司 | A kind of activation method of attapulgite |
-
1988
- 1988-04-29 CN CN 88105060 patent/CN1008074B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN1030365A (en) | 1989-01-18 |
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