CN101693205B - Preparation and application of dealkadiene hydrogenation protective agents - Google Patents
Preparation and application of dealkadiene hydrogenation protective agents Download PDFInfo
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- CN101693205B CN101693205B CN2009102177274A CN200910217727A CN101693205B CN 101693205 B CN101693205 B CN 101693205B CN 2009102177274 A CN2009102177274 A CN 2009102177274A CN 200910217727 A CN200910217727 A CN 200910217727A CN 101693205 B CN101693205 B CN 101693205B
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- hydrogenation protecting
- dialkene removal
- dealkadiene
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Abstract
The invention relates to preparation and application of dealkadiene hydrogenation protective agents. The preparation includes: choosing an appropriate alumina multi-hole ball and a rasching ring as carriers to be roasted in a high-temperature furnace and cooled to room temperature; dissolving nickel nitrate and ammonium metatungstate into deionized water to obtain tungsten nickel co-immersion liquor; immerging the roasted multi-hole ball and the roasted rasching ring to obtain protective agents; and drying the immerged protective agents and roasting the dried protective agents to obtain the dealkadiene hydrogenation protective agents. The application of the dealkadiene hydrogenation protective agents includes: the dealkadiene hydrogenation protective agents are placed on the topmost layer of a hydrogenation reactor bed; filling sequence from bottom to top of a reactor is set as main catalysts-disilication catalysts-deferrization catalysts- rasching ring dealkadiene hydrogenation protective agents-alumina multi-hole ball dealkadiene hydrogenation protective agents; and particle size and porosity of the dealkadiene hydrogenation protective agents ought to conform to grading loading requirements. The process for preparing the protective agents has simple technology, low cost, easy operation in loading and fine effect of preventing the pressure drop of the bed from increasing excessively quickly.
Description
Technical field:
The present invention relates to the protective agent in a kind of petrochemical technology, especially hydrogenation protecting agent.
Background technology:
Coker gasoline is a kind of inferior patrol, through doing the raw material of ethene, reformation and synthetic ammonia after the hydrofinishing.The coker gasoline hydrogen addition technology also has an evolution; Use the initial stage at the coker gasoline hydrogen addition technology; Because it is not enough to coking gasoline hydrogenation knowledge of regularity; The modal problem of coker gasoline hydrogenation plant is that bed and system's step-down increase are too fast, and stream time is short, needs shut-down to handle the problem of pressure drop increase.The hot-working petroleum that CN101029254A discloses after " method of hydrotreating of hot-working petroleum " heat exchange mixes in the stokehold with heat mixing hydrogen;, heating furnace gets into reactor then after being heated to reaction temperature; Heat time heating time at high temperature before having shortened hot-working petroleum and catalyst contacting, slowed down the intensity of hot-working petroleum in the independent heat exchange of heat exchanger, improved the efficiency of heating surface of stove simultaneously; Overcome alkadienes polymerization in heat exchanger and generated burnt matter, improved the thermal efficiency of heating furnace.CN100998952A disclose " a kind of coking gasoline hydrogenation refining catalyst and preparation method thereof " at first prepare catalyst carrier and different atomic ratios co-impregnated solution more than one; Next adopts secondary to flood altogether, and secondary drying, roasting are prepared into Hydrobon catalyst.Have that co-impregnated solution preparation is simple, be difficult for broken, good, the product yield advantages of higher of catalyst outward appearance in the roasting.Problems such as catalyst granules fragmentation in difficult, particle adhesion of high concentration co-impregnated solution preparation and the roasting process when having avoided once soaking altogether, outward appearance irregularity, product yield are low.Product adds that to have the saturated low temperature active of alkene a man-hour good in that coker gasoline is refining, can reduce the inlet temperature of reactor, carries out at a lower temperature that alkene is saturated, desulfurization, denitrification reaction, and coking speed is slow, and the regeneration period is long.Though the application of these patented technologies can significantly reduce the speed of coker gasoline hydrogenation plant system and bed step-down increase, the coker gasoline hydrogenation plant also uses protective agent.Existing protective agent has deferrization protective agent and desiliconization protective agent, and these protectant main effects are deferrization and desiliconization, stay the protective agent bed to iron and silicon objectionable impurities, and the protection major catalyst is avoided the pollution of silicon and iron.Have with the protective agent bed bigger space is arranged, also have certain effect preventing that bed step-down increase is too fast.Contain alkadienes in the coker gasoline, alkadienes is polymerization reaction take place under the catalytic action of acid, and the carrier of coker gasoline hydrogenation major catalyst, desiliconization agent and some deferrization agent all is an aluminium oxide; All has certain acid site; Coker gasoline touches these catalyst, also can carry out the alkadienes saturated reaction, but because the existence in acid site is arranged; Alkadienes also can carry out harmful side reaction of diene polymerization when the generation hydrogenation is saturated.Behind the diene polymerization, polymer is adsorbed on the carrier, because high temperature action generates burnt shape thing, the bed porosity is descended, and it is too fast to cause bed pressure drop to increase.
Summary of the invention:
The object of the invention just is the deficiency to above-mentioned prior art, and the preparation method of a kind of dialkene removal hydrogenation protecting agent is provided;
The purpose of this invention is to provide the agent of a kind of dialkene removal hydrogenation protecting;
Another object of the present invention provides the application of a kind of dialkene removal hydrogenation protecting agent.
Order of the present invention through following technology side by realizing:
The preparation of dialkene removal hydrogenation protecting agent comprises following order and step:
A, select diameter 9mm-15mm, hole count 3-7 aluminum oxide porous ball and internal diameter are 1mm-3mm, and length is that the Raschig ring of 5mm-7mm is made carrier, and respectively 800 ℃-1000 ℃ high temperature kiln roasting 1-3 hour, it is subsequent use to be cooled to room temperature;
B, preparation maceration extract are pressed mass fraction, are dissolved in 40 parts of deionized waters with 1 part of nickel nitrate and 2 parts of ammonium metatungstates, process tungsten nickel co-impregnated solution;
C, dipping are put into the maceration extract for preparing with baked porous ball or Raschig ring, and maceration extract will not have the porous ball or more than the Raschig ring 100mm, soaked 3-5 hour, made protective agent, emit raffinate and stay the inferior maceration extract usefulness of joining;
D, drying, the protective agent that dipping is good was dried 1-3 hour under 100 ℃-120 ℃ condition;
E, roasting, the protective agent that drying is crossed was processed the agent of dialkene removal hydrogenation protecting at 450 ℃ of-500 ℃ of following roasting 2-3 hours.
The application of dialkene removal hydrogenation protecting agent; The agent of dialkene removal hydrogenation protecting is contained in the superiors of hydrogenation reactor bed; Reactor filling from top to bottom is major catalyst → desilicification catalyst → deferrization catalyst → Raschig ring dialkene removal hydrogenation protecting agent → aluminum oxide porous ball dialkene removal hydrogenation protecting agent in proper order, and the granular size of dialkene removal hydrogenation protecting agent and porosity should meet the requirement of grading loading.
Order of the present invention can also be pressed through following technology side and realize:
The loading height of aluminum oxide porous ball dialkene removal hydrogenation protecting agent is not less than 200mm, and the loading height of Raschig ring dialkene removal hydrogenation protecting agent is 300-500mm.
Beneficial effect: the diene polymerization reaction does not take place in the agent of dialkene removal hydrogenation protecting, only carry out the diene hydrogenation saturated reaction, because the agent of dialkene removal hydrogenation protecting is seated in the topmost of reactor bed; After reactant gets into reactor; At first carry out the dialkene removal reaction, after alkadienes is sloughed or sloughed basically, contact deferrization catalyst, desilicification catalyst and major catalyst more successively; Even certain acidity is arranged on these catalyst and protective agent; These acidity also are that the completion catalytic action is needed, and the diene polymerization reaction can not take place, and have therefore prevented the too fast increase of bed pressure drop effectively.Protectant preparation technology is simple, and is with low cost, and it is too fast effective to have prevented that bed pressure drop from increasing.
The specific embodiment:
Below in conjunction with embodiment the present invention is done further detailed description:
The preparation of dialkene removal hydrogenation protecting agent comprises following order and step:
A, select diameter 9mm-15mm, hole count 3-7 aluminum oxide porous ball and internal diameter are 1mm-3mm, and length is that the Raschig ring of 5mm-7mm is made carrier, and respectively 800 ℃-1000 ℃ high temperature kiln roasting 1-3 hour, it is subsequent use to be cooled to room temperature;
B, preparation maceration extract are pressed mass fraction, are dissolved in 40 parts of deionized waters with 1 part of nickel nitrate and 2 parts of ammonium metatungstates, process tungsten nickel co-impregnated solution;
C, dipping are put into the maceration extract for preparing with baked porous ball or Raschig ring, and maceration extract will not have the porous ball or more than the Raschig ring 100mm, soaked 3-5 hour, made protective agent, emit raffinate and stay the inferior maceration extract usefulness of joining;
D, drying, the protective agent that dipping is good was dried 1-3 hour under 100 ℃-120 ℃ condition;
E, roasting, the protective agent that drying is crossed was processed the agent of dialkene removal hydrogenation protecting at 450 ℃ of-500 ℃ of following roasting 2-3 hours.
The application of dialkene removal hydrogenation protecting agent; The agent of dialkene removal hydrogenation protecting is contained in the superiors of hydrogenation reactor bed; Reactor filling from top to bottom is major catalyst → desilicification catalyst → deferrization catalyst → Raschig ring dialkene removal hydrogenation protecting agent → aluminum oxide porous ball dialkene removal hydrogenation protecting agent in proper order, and the granular size of dialkene removal hydrogenation protecting agent and porosity should meet the requirement of grading loading.
The loading height of aluminum oxide porous ball dialkene removal hydrogenation protecting agent is not less than 200mm, and the loading height of Raschig ring dialkene removal hydrogenation protecting agent is 300-500mm.
Embodiment 1
The preparation of dialkene removal hydrogenation protecting agent comprises following order and step:
A, select diameter 9mm, aluminum oxide porous ball that hole count is 3 and internal diameter are 1mm, and length is that the Raschig ring of 5mm is made carrier, and respectively 800 ℃ high temperature kiln roasting 1 hour, it is subsequent use to be cooled to room temperature;
B, preparation maceration extract are dissolved in the 40Kg deionized water with 1Kg nickel nitrate and 2Kg ammonium metatungstate, process tungsten nickel co-impregnated solution;
C, dipping are put into the maceration extract for preparing with baked porous ball or Raschig ring, and maceration extract will not have the porous ball or more than the Raschig ring 100mm, soaked 5 hours, made protective agent, emit raffinate and stay the inferior maceration extract usefulness of joining;
D, drying, the protective agent that dipping is good was dried 3 hours under 120 ℃ condition;
E, roasting, the protective agent that drying is crossed is processed the agent of dialkene removal hydrogenation protecting 500 ℃ of following roastings 3 hours.
The application of dialkene removal hydrogenation protecting agent; The agent of dialkene removal hydrogenation protecting is contained in the superiors of hydrogenation reactor bed; Reactor filling from top to bottom is major catalyst → desilicification catalyst → deferrization catalyst → Raschig ring dialkene removal hydrogenation protecting agent → aluminum oxide porous ball dialkene removal hydrogenation protecting agent in proper order, and the granular size of dialkene removal hydrogenation protecting agent and porosity should meet the requirement of grading loading.
The loading height of aluminum oxide porous ball dialkene removal hydrogenation protecting agent is not less than 200mm, and the loading height of Raschig ring dialkene removal hydrogenation protecting agent is 300mm.
Embodiment 2
The preparation of dialkene removal hydrogenation protecting agent comprises following order and step:
A, select diameter 15mm, aluminum oxide porous ball that hole count is 7 and internal diameter are 3mm, and length is that the Raschig ring of 6mm is made carrier, and respectively 900 ℃ high temperature kiln roasting 2 hours, it is subsequent use to be cooled to room temperature;
B, preparation maceration extract are dissolved in the 20Kg deionized water with 0.5Kg nickel nitrate and 1Kg ammonium metatungstate, process tungsten nickel co-impregnated solution;
C, dipping are put into the maceration extract for preparing with baked porous ball or Raschig ring, and maceration extract will not have the porous ball or more than the Raschig ring 100mm, soaked 4 hours, made protective agent, emit raffinate and stay the inferior maceration extract usefulness of joining;
D, drying, the protective agent that dipping is good was dried 2 hours under 110 ℃ 1 condition;
E, roasting, the protective agent that drying is crossed is processed the agent of dialkene removal hydrogenation protecting 480 ℃ of following roastings 2.5 hours.
The application of dialkene removal hydrogenation protecting agent; The agent of dialkene removal hydrogenation protecting is contained in the superiors of hydrogenation reactor bed; Reactor filling from top to bottom is major catalyst → desilicification catalyst → deferrization catalyst → Raschig ring dialkene removal hydrogenation protecting agent → aluminum oxide porous ball dialkene removal hydrogenation protecting agent in proper order, and the granular size of dialkene removal hydrogenation protecting agent and porosity should meet the requirement of grading loading.
The loading height of aluminum oxide porous ball dialkene removal hydrogenation protecting agent is not less than 200mm, and the loading height of Raschig ring dialkene removal hydrogenation protecting agent is 450mm.
Embodiment 3
The preparation of dialkene removal hydrogenation protecting agent comprises following order and step:
A, select diameter 15mm, aluminum oxide porous ball that hole count is 7 and internal diameter are 1mm, and length is that the Raschig ring of 7mm is made carrier, and respectively 1000 ℃ high temperature kiln roasting 1 hour, it is subsequent use to be cooled to room temperature;
B, preparation maceration extract are dissolved in the 200Kg deionized water with 5Kg nickel nitrate and 10Kg ammonium metatungstate, process tungsten nickel co-impregnated solution;
C, dipping are put into the maceration extract for preparing with baked porous ball or Raschig ring, and maceration extract will not have the porous ball or more than the Raschig ring 100mm, soaked 3 hours, made protective agent, emit raffinate and stay the inferior maceration extract usefulness of joining;
D, in dry, the protective agent that dipping is good was dried 1 hour under 100 ℃ condition;
E, roasting, the protective agent that drying is crossed is processed the agent of dialkene removal hydrogenation protecting 450 ℃ of following roastings 3 hours.
The application of dialkene removal hydrogenation protecting agent; The agent of dialkene removal hydrogenation protecting is contained in the superiors of hydrogenation reactor bed; Reactor filling from top to bottom is major catalyst → desilicification catalyst → deferrization catalyst → Raschig ring dialkene removal hydrogenation protecting agent → aluminum oxide porous ball dialkene removal hydrogenation protecting agent in proper order, and the granular size of dialkene removal hydrogenation protecting agent and porosity should meet the requirement of grading loading.
The loading height of aluminum oxide porous ball dialkene removal hydrogenation protecting agent is not less than 200mm, and the loading height of Raschig ring dialkene removal hydrogenation protecting agent is 500mm.
Claims (3)
1. the preparation of dialkene removal hydrogenation protecting agent is characterized in that, comprises following order and step:
A, select diameter 9mm-15mm, hole count 3-7 aluminum oxide porous ball and internal diameter are 1mm-3mm, and length is that the Raschig ring of 5mm-7mm is made carrier, and respectively 800 ℃-1000 ℃ high temperature kiln roasting 1-3 hour, it is subsequent use to be cooled to room temperature;
B, preparation maceration extract are pressed mass fraction, are dissolved in 40 parts of deionized waters with 1 part of nickel nitrate and 2 parts of ammonium metatungstates, process tungsten nickel co-impregnated solution;
C, dipping are put into the maceration extract for preparing with baked porous ball or Raschig ring, and maceration extract will not have the porous ball or more than the Raschig ring 100mm, soaked 3-5 hour, made protective agent, emit raffinate and stay the inferior maceration extract usefulness of joining;
D, drying, the protective agent that dipping is good was dried 1-3 hour under 100 ℃-120 ℃ condition;
E, roasting, the protective agent that drying is crossed was processed the agent of dialkene removal hydrogenation protecting at 450 ℃ of-500 ℃ of following roasting 2-3 hours.
2. according to the application of the described dialkene removal hydrogenation protecting of claim 1 agent; It is characterized in that; The agent of dialkene removal hydrogenation protecting is contained in the superiors of hydrogenation reactor bed; Reactor filling from top to bottom is major catalyst → desilicification catalyst → deferrization catalyst → Raschig ring dialkene removal hydrogenation protecting agent → aluminum oxide porous ball dialkene removal hydrogenation protecting agent in proper order, and the granular size of dialkene removal hydrogenation protecting agent and porosity should meet the requirement of grading loading.
3. according to the application of the described dialkene removal hydrogenation protecting of claim 2 agent, it is characterized in that the loading height of aluminum oxide porous ball dialkene removal hydrogenation protecting agent is not less than 200mm, the loading height of Raschig ring dialkene removal hydrogenation protecting agent is 300-500mm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102177274A CN101693205B (en) | 2009-10-14 | 2009-10-14 | Preparation and application of dealkadiene hydrogenation protective agents |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009102177274A CN101693205B (en) | 2009-10-14 | 2009-10-14 | Preparation and application of dealkadiene hydrogenation protective agents |
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| CN101693205B true CN101693205B (en) | 2012-04-18 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4448896A (en) * | 1981-06-02 | 1984-05-15 | Mitsubishi Chemical Ind., Ltd. | Hydrogenation catalyst for desulfurization and removal of heavy metals |
| CN1344781A (en) * | 2000-09-25 | 2002-04-17 | 中国石油化工股份有限公司 | Hydrogenation protecting catalyst and its prepn. |
| CN1362481A (en) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | Catalyst sorting and loading method |
| CN101152632A (en) * | 2006-09-29 | 2008-04-02 | 中国石油化工股份有限公司 | Hydroactivity protector and its production |
-
2009
- 2009-10-14 CN CN2009102177274A patent/CN101693205B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4448896A (en) * | 1981-06-02 | 1984-05-15 | Mitsubishi Chemical Ind., Ltd. | Hydrogenation catalyst for desulfurization and removal of heavy metals |
| CN1344781A (en) * | 2000-09-25 | 2002-04-17 | 中国石油化工股份有限公司 | Hydrogenation protecting catalyst and its prepn. |
| CN1362481A (en) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | Catalyst sorting and loading method |
| CN101152632A (en) * | 2006-09-29 | 2008-04-02 | 中国石油化工股份有限公司 | Hydroactivity protector and its production |
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| CN101693205A (en) | 2010-04-14 |
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Effective date of registration: 20161026 Address after: 116000 A, building -A7-1, colorful city, Dalian economic and Technological Development Zone, Liaoning, China Patentee after: Dalian Engineering Construction Co., Ltd. Address before: Our high tech Development Zone in Jilin province Changchun 130012 Street No. 286 Patentee before: Changchun Huigong Purifying Industry Co., Ltd. |
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