CN1048192C - Catalyst for recovering TiO2 base sulfur and preparing method thereof - Google Patents
Catalyst for recovering TiO2 base sulfur and preparing method thereof Download PDFInfo
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- CN1048192C CN1048192C CN95110393A CN95110393A CN1048192C CN 1048192 C CN1048192 C CN 1048192C CN 95110393 A CN95110393 A CN 95110393A CN 95110393 A CN95110393 A CN 95110393A CN 1048192 C CN1048192 C CN 1048192C
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Abstract
The present invention relates to a novel TiO2 base catalyst for recovering sulfur. The novel TiO2 base catalyst for recovering sulfur is composed of the chemical components: 85% to 89% of TiO2, 10% to 14% of CaSO4 and 0.5% to 5% of CaO; industrial metatitanic acid produced by a sulfuric acid method is directly used as the starting material of TiO2 to prepare the novel TiO2 base catalyst for recovering sulfur. The preparation process of the present invention comprises the steps, such as drying, pulverizing, kneading, bar extruding, roasting, etc., wherein the CaO used as an accelerative activator and a mechanical strength improver is added in the shape of calcium nitrate; in addition, an extrusion aid is added into the present invention, the total amount of the extrusion aid accounts for 0.5 to 10% of the catalyst weight. Compared with the prior art, the novel TiO2 base catalyst for recovering sulfur of the present invention has higher activity and higher mechanical strength.
Description
The present invention relates to the H that from the oil and natural gas process, produces
2The Catalysts and its preparation method of Recovered sulphur in the S gas.
In the oil and natural gas process, produce a large amount of H
2S gas in order to protect environment and to reclaim elementary sulfur, industrially generally adopts claus process to handle to contain H
2The sour gas of S, its reaction equation is as follows:
Carry out in high temperature combustion furnace above-mentioned reaction (1) and (2), at catalytic reaction zone, except react (2), also descends the hydrolysis of routine organic sulfur compound:
As a kind of well behaved catalyst for recovering sulfur, all should have higher activity and stable to reaction (2), (3) and (4), many researchs and industrial practice show, Al
2O
3Be a kind of well behaved catalyst for recovering sulfur, yet, mainly be " to leak O in the technical process owing to be subjected to the restriction of operating condition
2" existence, can cause Al
2O
3The catalyst sulfuric acid salinization is poisoned, and the result causes CS before this
2With the COS percent hydrolysis, be H then
2The S conversion ratio descends significantly.
In order to prevent the sulfation poisoning, developed a kind of non-Al abroad
2O
3The CRS-31 TiO of base
2Extruded catalyst, according to G.B.P2,122,579 introduce, and this catalyst is to " leaking O
2" insensitive, have very high catalytic activity.
Generally with TiO
2Be main carrier or catalyst with traditional extruded moulding technology, the mechanical strength of its product is difficult to satisfactory, therefore always adopt usually and in material, add boric acid, silicate, binding agents such as aluminium colloidal sol, or adding alum thing, borate, adhesive accelerants such as phosphate improve intensity, but the result is also undesirable, not to stop up duct or topped activity of such catalysts surface because after roasting, transform into glass state material, exactly because consumption has too much changed the physical and chemical performance of catalyst or carrier, even the auxiliary agent itself that adds sometimes is exactly a kind of catalyst poison.V for example
2O
5, because of promoting the SO in the claus process
2Catalysis becomes SO
3, and cause the Al in downstream
2O
3The catalyst sulfuric acid salinization is poisoned.
At U.S.P 4,113, in 660, by in metatitanic acid, adding BaCl
2, add HCl simultaneously and make it that peptization take place, form metatitanic acid colloidal sol or gel, in the presence of metatitanic acid colloidal sol or gel, roasting is a kind of with TiO then
2Be to transform into TiO after main or the roasting
2Material, though can improve effectively
TiO
2The mechanical strength of extruded catalyst, but the Cl that in said process, introduces
-1To equipment, especially high-temperature roasting equipment has serious corrosiveness.
The CRS-31 catalyst is a kind of TiO that combines with alkali earth metal sulfate that adopts
2Extruded catalyst, though have higher mechanical strength, its mechanical strength stability, promptly the mechanical strength under claus process hydro-thermal atmospheric condition is not satisfactory.Existing newspaper is logical, the TiO that has unloaded after turning round on the commercial plant 14 months
2Extruded catalyst declines by a big margin through detect finding its mechanical strength, only is original 1/3.
The object of the invention provides a kind of new Ti O
2The base catalyst for recovering sulfur, it not only has higher mechanical strength and mechanical strength stability, abrasion resistance properties preferably, but also have active and anti-" the leakage O of very high Crouse
2" poisoning performance.
Characteristics of the present invention are directly to adopt the industrial metatitanic acid of Production By Sulfuric Acid Process as TiO
2Starting material.TiO in the catalyst
2Content (m/m) is 85%-89%, CaSO
4Content (m/m) is 10%-14%, has added CaO in addition, and its content (m/m) is 0.5-5%.The CaO that is added has not only promoted the claus reaction activity of catalyst, organic sulfur compound hydrolysis reaction activity especially, but also collaborative CaSO
4The mechanical strength and the mechanical strength stability of catalyst have been improved together.
Another feature of the present invention is in order to improve the agent bar machine-shaping property of metatitanic acid material, also to have added a kind of composite molding additive.Extrusion aid commonly used has field mountain valley with clumps of trees and bamboo powder, starch and various surfactant, and carboxymethyl or ethyl cellulose, polyvinyl alcohol, or a kind of or its mixture in the organic polymer such as polyacrylamide.The composite molding additive of forming by atoleine and Triton X-100 that the present invention adopts, both weight ratios are 1-5: 1, consumption is the 0.5-10% of catalyst weight.
The evaluation test of this activity of such catalysts is adopted and is accelerated aging test method, turns round 30 hours continuously under the commercial plant atmospheric condition of simulation.Wherein " slight aging " is earlier catalyst to be carried out sulfation poisoning preliminary treatment, and condition is bubbling air and SO under 450 ℃ of bed temperatures
2Ratio is the mist of 7: 3 (body), with 700h
-1Air speed running 2 hours, and then measure its hydrolysis reaction activity and claus reaction activity; " harsh aging " processing method is identical with it with program, just must its specific area be descended, and then carry out sulfation poisoning preliminary treatment earlier with the further high-temperature roasting of catalyst.According to the data introduction, " slight aging " is equivalent to catalyst and turned round continuously on commercial plant 2000 hours, and " harsh aging " then is equivalent to the 3--4 year of having turned round.
The activity rating that " slight aging " handles rear catalyst the results are shown in Table 1.
Table 1. catalyst " slight aging " is handled back activity rating result
| Catalyst | CS 2Percent hydrolysis V% | H 2S conversion ratio V% |
| Catalyst of the present invention | 86.8 | 70.3 |
| CRS--31 | 81.7 | 67.6 |
* annotate: the catalyst activity appreciation condition is 330 ± 3 ℃ of bed temperatures; Gas composition, H
2S 6V%, SO
24V%, CS
21V%, O
20.2V%, H
2O 28V%, all the other are N
2Air speed 2000h
-1
After " harsh aging " handled, the activity of such catalysts evaluation result saw Table 2, and appreciation condition is with preceding identical.
Table 2. catalyst " harsh aging " is handled back activity rating result
| Catalyst | CS 2Percent hydrolysis V% | H 25 conversion ratio V% |
| Catalyst of the present invention | 86.4 | 68.5 |
| CRS--31 | 80.4 | 66.5 |
The anti-of catalyst " leaked O
2" poisoning performance can be by investigating O
2The relatively more responsive hydrolysis reaction activity of content compares, and activity rating the results are shown in Table 3, during test, and the O in the unstripped gas
2The content scope is 800--20,000PPM, and other condition is with preceding identical, and in the device operation process, every interval changed once in 4 hours " leaks O
2" concentration, being changed to 800,2,000,5,000,10,000 and 20 successively, 000PPM stops into O after turning round 20 hours continuously
2, and then turned round continuously 8 hours.
Table 3. catalyst tolerates " is leaked O
2" poisoning performance activity rating result
| Catalyst | CS 2Percent hydrolysis V% | |||||
| 800PPM | 2,000PPM | 5,000PPM | 10,000PPM | 20,000PPM | Stop into O 2Behind the 8h | |
| Catalyst of the present invention | 87.4 | 87.3 | 82.7 | 75.9 | 72.6 | 87.3 |
| CR5-31 | 82.8 | 82.7 | 78.1 | 72.5 | 68.8 | 82.8 |
Preparation of Catalyst
Embodiment 1.
This catalyst is by TiO
2, CaSO
4Form with CaO.TiO wherein
2Content is 88% (m/m), CaSO
4Content is 10% (m/m), and CaO content is 2% (m/m).
Preparation worker gas is as follows: will contain SO
2Industrial metatitanic acid in 120 ℃ of dryings 4 hours, wherein SO
2With TiO
2Weight ratio be 0.08.After being crushed to 180 orders, add Ca (NO
3)
2Solution, wherein Ca and TiO
2Weight ratio be 0.034.The liquid-solid ratio of said mixture material is 44: 56, mix pinch 2 hours after, be extruded moulding in the orifice plate of 4.5mm at diameter, through 120 ℃ of dryings after 4 hours, under the flow air atmospheric condition, in 500 ℃ of roastings 2 hours.
According to the catalyst of embodiment 1 preparation, its main physical and chemical performance test result is listed in table 4.
The main physical and chemical performance test result of table 4. catalyst
| The physical and chemical performance catalyst | Specific area m 2/g | Specific pore volume ml/g | Mechanical strength N/Cm | Mechanical strength N/Cm behind the boiling test | Mechanical strength N/Cm after the high-temperature water heat treatment | Wear rate % (m/m) |
| Catalyst of the present invention | 112 | 0.215 | 99 | 80 | 63 | 0.85 |
| CRS-31 | 101 | 0.196 | 71 | 62 | 42 | 1.35 |
Wherein:
(1) specific area adopts distant Q1750-84 ethanol drier method to measure.
(2) the following specific pore volume of 40nm adopts distant Q1750-84 ethanol drier to measure.
(3) mechanical strength is measured on the QCY-602 type strength tester that basic industry research institute in Dalian makes.
(4) boiling test system is placed on former granularity catalyst earlier and boils 2 hours in the distilled water, take out air-dry after, 120 ℃ of dryings are 2 hours again, measure its mechanical strength then.
(5) hydrothermal treatment consists system is placed on former granularity catalyst in the tubular reactor, feeds N at 500 ℃ of temperature conditions
2With the water vapour proportion of composing be the mist of 7: 3 (body), with 1000h
-1Its mechanical strength is measured in air speed running 30 hours then.
(6) wear test system with former granularity catalyst 120 ℃ of dryings 2 hours, after taking by weighing 100g weight, placing diameter is 20cm, highly is in the stainless steel airtight container of 10cm, with 60r/min rotating speed rotation 30 minutes, measure the weight of the catalyst fines that produces by friction.
Embodiment 2.
The chemical composition and the preparation technology of catalyst are the same, the composite molding additive that just adds atoleine and Triton X-100 composition at kneading process, its addition is 1% of a total catalyst weight, and wherein the weight ratio of atoleine and Triton X-100 is 2: 1.
According to the catalyst of example 2 preparations, the composite molding additive is shown in the influence of table 5 table 5. moulding additive to catalyst extrusion machine-shaping property to the influence of catalyst extrusion machine-shaping property
| Catalyst | The extrusion machine-shaping property | Pore volume ml/g |
| Embodiment 1 | Material can intermittently be processed extrusion, extrudate smooth surface | 0.281 |
| Embodiment 2 | Material can be processed extrusion continuously, extrudate surface smoother | 0.361 |
Claims (4)
1. titanium deoxide catalyst that is used for Recovered sulphur from the hydrogen sulfide that the oil and natural gas process produces, the chemical composition that it is characterized in that catalyst is TiO
2Be 85～89 weight %, calcium sulfate is that 10～14 weight % and calcium oxide are 0.5～5 weight %.
2. the described Preparation of catalysts method of claim 1 comprises drying, pulverizing, kneading, extrusion and calcination steps, it is characterized in that directly adopting the industrial metatitanic acid of Production By Sulfuric Acid Process as TiO
2Starting material, and add CaO as accelerative activator and mechanical strength promoting agent.
3. by the described method of claim 2, it is characterized in that CaO is that form with calcium nitrate adds at kneading step.
4. by the described method of claim 2, it is characterized in that having added the compound extrusion aid of being made up of atoleine and Triton X-100 in kneading process, both weight ratios are 1～5: 1, and total consumption is 0.5～10% of a catalyst weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95110393A CN1048192C (en) | 1995-03-16 | 1995-03-16 | Catalyst for recovering TiO2 base sulfur and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95110393A CN1048192C (en) | 1995-03-16 | 1995-03-16 | Catalyst for recovering TiO2 base sulfur and preparing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1131058A CN1131058A (en) | 1996-09-18 |
| CN1048192C true CN1048192C (en) | 2000-01-12 |
Family
ID=5077785
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95110393A Expired - Lifetime CN1048192C (en) | 1995-03-16 | 1995-03-16 | Catalyst for recovering TiO2 base sulfur and preparing method thereof |
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| Country | Link |
|---|---|
| CN (1) | CN1048192C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100369667C (en) * | 2005-10-14 | 2008-02-20 | 南京工业大学 | Nanometer titanium dioxide forming substances and preparation thereof |
| CN107469803B (en) * | 2016-06-07 | 2020-05-12 | 中国石油化工股份有限公司 | Sulfur recovery catalyst and preparation method thereof |
| CN106807435B (en) * | 2017-01-13 | 2019-10-25 | 山东齐鲁科力化工研究院有限公司 | A kind of titanium-based catalyst for recovering sulfur and preparation method thereof |
| CN109126847B (en) * | 2018-08-04 | 2021-10-15 | 山东迅达化工集团有限公司 | Preparation method of iron oxide and titanium dioxide composite sulfur recovery catalyst |
| CN109126755B (en) * | 2018-08-04 | 2021-07-23 | 山东迅达化工集团有限公司 | Preparation method of titanium dioxide-based sulfur recovery catalyst |
| CN109126830B (en) * | 2018-08-04 | 2021-07-23 | 山东迅达化工集团有限公司 | Preparation method of titanium dioxide-based sulfur recovery catalyst |
| CN109126831B (en) * | 2018-08-04 | 2021-07-23 | 山东迅达化工集团有限公司 | Iron oxide and titanium dioxide composite sulfur recovery catalyst and preparation method thereof |
| CN111203203B (en) * | 2020-02-16 | 2022-05-27 | 山东迅达化工集团有限公司 | Calcium sulfate fiber reinforced titanium oxide carrier or catalyst and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4113660A (en) * | 1975-12-23 | 1978-09-12 | Sakai Chemical Industry Co., Ltd. | Production of shaped catalysts or carriers comprising titanium oxides |
| GB2133597A (en) * | 1983-01-03 | 1984-07-25 | Analog Devices Inc | Temperature compensated logarithmic circuit |
| JPS59183830A (en) * | 1983-03-25 | 1984-10-19 | Nippon Steel Chem Co Ltd | Production of iron oxide containing catalyst |
| JPS59186929A (en) * | 1983-04-05 | 1984-10-23 | Asahi Chem Ind Co Ltd | Production of cycloolefin |
| CN1045763A (en) * | 1989-03-23 | 1990-10-03 | 国际壳牌研究有限公司 | Titania extrudates |
-
1995
- 1995-03-16 CN CN95110393A patent/CN1048192C/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4113660A (en) * | 1975-12-23 | 1978-09-12 | Sakai Chemical Industry Co., Ltd. | Production of shaped catalysts or carriers comprising titanium oxides |
| GB2133597A (en) * | 1983-01-03 | 1984-07-25 | Analog Devices Inc | Temperature compensated logarithmic circuit |
| JPS59183830A (en) * | 1983-03-25 | 1984-10-19 | Nippon Steel Chem Co Ltd | Production of iron oxide containing catalyst |
| JPS59186929A (en) * | 1983-04-05 | 1984-10-23 | Asahi Chem Ind Co Ltd | Production of cycloolefin |
| CN1045763A (en) * | 1989-03-23 | 1990-10-03 | 国际壳牌研究有限公司 | Titania extrudates |
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| Publication number | Publication date |
|---|---|
| CN1131058A (en) | 1996-09-18 |
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