CN1342601A - Process for preparing V catalyst used to prepare low-temp sulfuric acid - Google Patents

Process for preparing V catalyst used to prepare low-temp sulfuric acid Download PDF

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CN1342601A
CN1342601A CN 01134109 CN01134109A CN1342601A CN 1342601 A CN1342601 A CN 1342601A CN 01134109 CN01134109 CN 01134109 CN 01134109 A CN01134109 A CN 01134109A CN 1342601 A CN1342601 A CN 1342601A
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low
diatomite
temperature
temp
sulfuric acid
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CN1159210C (en
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田先国
张秋菊
苏东辉
陈海波
黄建明
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Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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Research Institute of Nanjing Chemical Industry Group Co Ltd
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Abstract

A low-temp. V-catalyst for preparing low-temp. type sulfuric acid is prepared by adding low-temp. activator (soluble Cs or Na salt and phosphorus-contained compound) and using different methods to add assistant. Its advantage is high low-temp. activity.

Description

A kind of manufacture method of V catalyst used to prepare low-temp sulfuric acid
Technical field: the invention belongs to catalysis technical field, be specifically related to a kind of manufacture method of V catalyst used to prepare low-temp sulfuric acid.
Background technology: vanadium catalyst is used for sulfuric acid production plant with SO 2Oxidation conversion is SO 3General traditional vanadium catalyst is vanadium-potassium (sodium)-silicon system, two kinds of middle warm type and low temperature modifications are arranged, and middle temperature type vanadium catalyst generally is used for, two, three section of convertor, and the service temperature general requirement is higher than 420 ℃, be no more than 600 ℃, it is active to have middle preferably temperature; Low-temperature type vanadium catalyst generally is used for one section top of convertor and four sections, five sections, and the service temperature general requirement is higher than 410 ℃, has better low temperature activity, helps improving SO in the sulfuric acid conversion device 2Be converted into SO 3Total conversion rate.In the sulfuric acid production plant of double conversion and double absorption flow process combination loading traditional in, low-temperature type vanadium catalyst, can make SO 2Final transformation efficiency reaches 99.5%.
The existing manufacture method of vanadium catalyst:
Vanadium catalyst is generally vanadium-potassium-silicon system at present, and low-temperature type vanadium catalyst is vanadium-potassium-sodium-silicon system.Manufacture method be with raw material diatomite through the making beating, acid treatment, overanxious washing and drying make terra silicea purificata; KOH is dissolved with steam, and and V 2O 5Under boiling condition, heat makes satisfactory KVO 3With KOH mixing solutions (being called for short vanadium water), then vanadium water is made V with the sulfuric acid neutralization 2O 5And K 2SO 4The colloidal precipitation thing will mix in the adding rollers such as colloidal precipitation thing and auxiliary agent, terra silicea purificata to scale, rolls closely, becomes the plasticity-material, again through extrusion, drying, roasting, sieve and operation such as packing is made vanadium catalyst.Vanadium catalyst with this method preparation can satisfy the needs of gas washing in SA production substantially, but uses traditional low-temperature type vanadium catalyst will satisfy SO 2It is difficult that total conversion rate reaches more than 99.8%.
Summary of the invention: the objective of the invention is to propose a kind of manufacture method of low-temperature type vanadium catalyst, this catalyzer has higher low temperature active and thermostability than traditional low-temperature type vanadium catalyst, can satisfy higher SO 2Total conversion rate needs.
The low-temperature type vanadium catalyst that the inventive method is produced has better low-temperature catalyzed performance than traditional low-temperature type vanadium catalyst, low 20~40 ℃ of the more traditional vanadium catalyst of combustion initiation temperature, service temperature can be reduced to 380~390 ℃ from 410~420 ℃, this catalyzer is substituted low-temperature type vanadium catalyst be used for gas washing in SA production, can make the SO of the sulfuric acid apparatus of double conversion and double absorption flow process 2Final transformation efficiency reaches 99.8%, and reduced the service temperature of one section of convertor, helps high density SO 2Conversion, adapted to that sulfuric acid apparatus maximizes and the development of acid production with sulphur, use this catalyzer at the convertor latter end, improved the total conversion rate in the convertor, reduced SO in the tail gas 2Concentration, satisfied the environmental requirement of increasingly stringent.
The present invention is achieved like this, and by adding the low-temperature activation agent, improves the low temperature active of vanadium catalyst, reduces combustion initiation temperature.It mainly comprises following content: the low-temperature activation agent is soluble metal cesium salt, sodium salt, P contained compound, and addition manner is for adding when mixed grind or it being joined in the vanadium water; The catalyst formulation weight percent is V 2O 55.0~8.5% K 2O/V 2O 52.5~4.5 Na 2SO 41.0~15.0% Cs 2SO 41.0~15.0% P 2O 51.0~5.0% all the other be diatomite.
The used soluble metal cesium salt of the present invention can be a kind of in cesium sulfate, cesium carbonate, the cesium nitrate, also can be two or three mixture wherein; Sodium salt is a sodium sulfate; P contained compound can be a kind of in phosphoric acid, ammonium phosphate, the sodium acid phosphate salt; Diatomite can be a kind of in Linqu, Shandong diatomite, northeast long white diatomite, Shengxian County, Zhejiang diatomite and the Yunnan Xun Dian diatomite.
The vanadium catalyst of the present invention preparation is applicable to the one section top and the two transfer part branches of convertor of the sulfuric acid production plant of double conversion and double absorption flow process.
Embodiment: further specify content of the present invention below in conjunction with embodiment:
Embodiment 1-1
Sample prescription V 2O 56.5% K 2O/V 2O 52.7 Na 2SO 413.7% P 2O 51.0% all the other be diatomite; Adopt traditional processing technology, Linqu, Shandong diatomite through wet concentration, acid treatment, overanxious washing and drying, is made the Shandong terra silicea purificata; KOH is dissolved with steam, and and V 2O 5Under boiling condition, heat makes K 2O/V 2O 5Be 2.7 KVO 3With KOH mixing solutions (being called for short vanadium water), then a certain amount of vanadium water is made V with the sulfuric acid neutralization 2O 5And K 2SO 4The colloidal precipitation thing is to scale with colloidal precipitation thing and Na 2SO 4, H 3PO 4, mix in the adding roller such as Shandong terra silicea purificata, add water-powered roller and compress closely, become the plasticity-material, again through extrusion, drying, roasting, sieve and operation such as packing is made vanadium catalyst.
Embodiment 1-2
Sample prescription V 2O 56.5% K 2O/V 2O 52.7 Na 2SO 48.0% Cs 2SO 42.0% P 2O 51.0% all the other be diatomite; Adopt traditional processing technology.
Embodiment 1-3
Sample prescription V 2O 56.5% K 2O/V 2O 52.7 Na 2SO 46.0% Cs 2SO 44.0% P 2O 51.0% all the other be diatomite; Adopt traditional processing technology.
Embodiment 1-4
Sample prescription V 2O 56.5% K 2O/V 2O 52.7 Na 2SO 48.0% Cs 2SO 42.0% P 2O 51.0% all the other be diatomite; Employing adds the low-temperature activation agent in vanadium water.
Embodiment 1-5
Sample prescription V 2O 56.5% K 2O/V 2O 52.7 Na 2SO 44.0% Cs 2SO 410.0% P 2O 51.0% all the other be diatomite; Employing adds the low-temperature activation agent in vanadium water.
Embodiment 1-6
Sample prescription V 2O 57.0% K 2O/V 2O 52.7 Na 2SO 42.0% Cs 2SO 410.0% P 2O 51.0% all the other be diatomite; Employing adds the low-temperature activation agent in vanadium water.
Sample test
Catalyst sample: granularity is
Figure A0113410900061
5 * 6~6.5mm.The active testing condition:
Convertor: adopt the jacketed type single tube reactor, its caliber is 36 * 2mm, the temperature thermocouple cover
Pipe is positioned at the center of convertor, and its caliber is 8 * 1.5mm;
Catalyzer loading amount: 30ml;
Catalyst grain size: 6~6.5mm;
Space velocity: 3600h;
Air inlet SO 2Percent by volume: be air surplus in the of 10 ± 1%;
System pressure: normal pressure;
Active detected temperatures: 390 ℃, 410 ℃;
Heat resisting temperature and time: 600 ℃ of 5h;
With SO 2Transformation efficiency represent active height.
Active testing the results are shown in table one, and wherein sample 1-1 is traditional low-temperature type vanadium catalyst, and sample 1-2,1-3,1-4,1-5,1-6 are ultralow warm type vanadium catalyst
Table one active testing result
The sample example Active (heat-resisting back SO 2Transformation efficiency) % Relative value
????390℃ ????410℃ ????390℃ ????410℃
????1-1 ????22.0 ????38.1 ????1 ????1
????1-2 ????29.5 ????47.4 ????1.34 ????1.24
????1-3 ????27.9 ????48.9 ????1.27 ????1.28
????1-4 ????28.1 ????47.4 ????1.27 ????1.24
????1-5 ????29.5 ????45.6 ????1.34 ????1.20
????1-6 ????32.5 ????56.1 ????1.48 ????1.47
Can find out that by test result the low temperature active of the ultralow warm type vanadium catalyst of employing the inventive method preparation shows that apparently higher than traditional low-temperature type vanadium catalyst the performance of the vanadium catalyst that the present invention prepares is significantly improved, and can satisfy higher SO 2The total conversion rate requirement.

Claims (2)

1. the manufacture method of a V catalyst used to prepare low-temp sulfuric acid, by adding the low-temperature activation agent, improve the low temperature active of vanadium catalyst, reduce combustion initiation temperature, it is characterized in that the low-temperature activation agent is soluble metal cesium salt, sodium salt, P contained compound, addition manner is for adding when mixed grind or it being joined in the vanadium water, and its formulation weight per-cent is V 2O 55.0~8.5% K 2O/V 2O 52.5~4.5Na 2SO 41.0~15.0% Cs 2SO 41.0~15.0% P 2O 51.0~5.0% all the other be diatomite.
2. manufacture method of V catalyst used to prepare low-temp sulfuric acid according to claim 1, it is characterized in that soluble metal cesium salt in the low-temperature activation agent can be wherein a kind of of cesium sulfate, cesium carbonate, cesium nitrate, also can be two or three mixture wherein; Sodium salt is a sodium sulfate; P contained compound can be a kind of in phosphoric acid, ammonium phosphate, the sodium acid phosphate; Diatomite can be a kind of in Linqu, Shandong diatomite, northeast long white diatomite, Shengxian County, Zhejiang diatomite and the Yunnan Xun Dian diatomite.
CNB011341092A 2001-10-30 2001-10-30 Process for preparing V catalyst used to prepare low-temp sulfuric acid Expired - Fee Related CN1159210C (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1299973C (en) * 2002-12-11 2007-02-14 南化集团研究院 New Vanadium catalyst for low-temperature sulfuric acid production and its prepn
CN101041131B (en) * 2006-03-20 2010-09-08 襄樊市精信催化剂有限责任公司 Wide temperature type sulfur dioxide oxidation system producing aulfuric acid and the preparing method
CN101462048B (en) * 2008-06-21 2011-08-24 康喆 Vanadium catalyst containing tungsten for producing acid by oxidation and preparation method thereof
CN102350367A (en) * 2011-08-30 2012-02-15 开封市三丰催化剂有限责任公司 Production method of sulfuric acid catalyst by oxidizing sulfur dioxide
CN103506143A (en) * 2012-06-21 2014-01-15 中国石油化工股份有限公司 Low-temperature type vanadium catalyst for preparation of sulfuric acid by wet conversion
CN104741110A (en) * 2015-03-25 2015-07-01 襄阳市精信催化剂有限责任公司 Process for preparing sulfuric acid catalyst by oxidation of sulfur dioxide
CN105126861A (en) * 2015-09-07 2015-12-09 吉林省天元硅藻科技有限公司 Sulfuric acid catalyst prepared through middle and low temperature hydrogen sulfide wetting method and preparation method therefor
CN109759052A (en) * 2019-02-14 2019-05-17 襄阳市精信催化剂有限责任公司 A kind of preparation method of sulfuric acid catalyst by oxidizing sulfur dioxide
CN111036242A (en) * 2018-10-12 2020-04-21 中国石油化工股份有限公司 Vanadium-based catalyst for preparing sulfuric acid by wet conversion

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1299973C (en) * 2002-12-11 2007-02-14 南化集团研究院 New Vanadium catalyst for low-temperature sulfuric acid production and its prepn
CN101041131B (en) * 2006-03-20 2010-09-08 襄樊市精信催化剂有限责任公司 Wide temperature type sulfur dioxide oxidation system producing aulfuric acid and the preparing method
CN101462048B (en) * 2008-06-21 2011-08-24 康喆 Vanadium catalyst containing tungsten for producing acid by oxidation and preparation method thereof
CN102350367A (en) * 2011-08-30 2012-02-15 开封市三丰催化剂有限责任公司 Production method of sulfuric acid catalyst by oxidizing sulfur dioxide
CN102350367B (en) * 2011-08-30 2013-08-14 开封市三丰催化剂有限责任公司 Production method of sulfuric acid catalyst by oxidizing sulfur dioxide
CN103506143A (en) * 2012-06-21 2014-01-15 中国石油化工股份有限公司 Low-temperature type vanadium catalyst for preparation of sulfuric acid by wet conversion
CN104741110A (en) * 2015-03-25 2015-07-01 襄阳市精信催化剂有限责任公司 Process for preparing sulfuric acid catalyst by oxidation of sulfur dioxide
CN105126861A (en) * 2015-09-07 2015-12-09 吉林省天元硅藻科技有限公司 Sulfuric acid catalyst prepared through middle and low temperature hydrogen sulfide wetting method and preparation method therefor
CN111036242A (en) * 2018-10-12 2020-04-21 中国石油化工股份有限公司 Vanadium-based catalyst for preparing sulfuric acid by wet conversion
CN109759052A (en) * 2019-02-14 2019-05-17 襄阳市精信催化剂有限责任公司 A kind of preparation method of sulfuric acid catalyst by oxidizing sulfur dioxide
CN109759052B (en) * 2019-02-14 2021-12-07 襄阳市精信催化剂有限责任公司 Preparation method of catalyst for preparing sulfuric acid by oxidizing sulfur dioxide

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