CN104646071B - A kind of clean method for preparing of carrier of hydrogenating catalyst - Google Patents
A kind of clean method for preparing of carrier of hydrogenating catalyst Download PDFInfo
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- CN104646071B CN104646071B CN201310584275.XA CN201310584275A CN104646071B CN 104646071 B CN104646071 B CN 104646071B CN 201310584275 A CN201310584275 A CN 201310584275A CN 104646071 B CN104646071 B CN 104646071B
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- acid
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- oxide
- adhesive
- carrier
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- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002253 acid Substances 0.000 claims abstract description 43
- 239000000853 adhesive Substances 0.000 claims abstract description 31
- 230000001070 adhesive effect Effects 0.000 claims abstract description 31
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 24
- 150000007524 organic acids Chemical class 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 41
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 239000003292 glue Substances 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011959 amorphous silica alumina Substances 0.000 claims description 5
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910021417 amorphous silicon Inorganic materials 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000000243 solution Substances 0.000 description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 15
- 229910017604 nitric acid Inorganic materials 0.000 description 15
- 238000005984 hydrogenation reaction Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000011148 porous material Substances 0.000 description 9
- 238000007493 shaping process Methods 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 8
- 235000015165 citric acid Nutrition 0.000 description 7
- 150000007522 mineralic acids Chemical class 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 241000219793 Trifolium Species 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000001935 peptisation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 241001101998 Galium Species 0.000 description 2
- 235000014820 Galium aparine Nutrition 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 241000612118 Samolus valerandi Species 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 235000015110 jellies Nutrition 0.000 description 2
- 239000008274 jelly Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- CKQGJVKHBSPKST-UHFFFAOYSA-N [Ni].P#[Mo] Chemical compound [Ni].P#[Mo] CKQGJVKHBSPKST-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- IXSZQYVWNJNRAL-UHFFFAOYSA-N etoxazole Chemical compound CCOC1=CC(C(C)(C)C)=CC=C1C1N=C(C=2C(=CC=CC=2F)F)OC1 IXSZQYVWNJNRAL-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- -1 nickel aluminate Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a kind of preparation method of catalyst carrier, including：Mixed acid solution is prepared, phosphoric acid and organic acid are contained in mixed acid solution；Above-mentioned mixed acid solution mixes with oxide precursor, prepares adhesive；Adhesive mix with catalyst support material powder, be then molded, dried, be calcined, obtain catalyst carrier.Compared with prior art, the present invention provides a kind of catalyst carrier preparation method, by using Compound-acid, contaminative exhaust emissions in catalyst carrier production process is solved the problems, such as, while ensure that the performance of catalyst carrier.
Description
Technical field
The present invention relates to a kind of preparation method of supported catalyst agent carrier, especially without NO in preparation processxDischarge
The preparation method of carrier of hydrogenating catalyst.
Background technology
Become weight year by year with crude quality, be deteriorated, environmental regulation is increasingly strict, and market is continuous to the demand of clear gusoline
Increase so that the hydrogen addition technology of production clean fuel is increasingly widely applied.Distillate hydrogenation treatment refers to high temperature high
There is hydrodesulfurization, hydrodenitrogeneration, hydrogenation deoxidation, HDM and not on catalyst surface in pressure, feedstock oil and hydrogen
The catalytic reactions such as saturated hydrocarbons hydrogenation saturation.Because crude quality is deteriorated year by year, and refinery starts universal to increase economic efficiency
Using crude oil deep vacuum distillation technology so that doing for vacuum distillate has brought up to more than 600 DEG C by original 520 DEG C, and its is close
Spend increasing, boiling range more and more higher, contained hydrocarbon molecule molecular weight is increasing, impurity content is also more and more, especially
The baroque condensed-nuclei aromatics compounds content of sulfur-bearing, nitrogen impurity is greatly increased, and the abjection difficulty of impurity is greatly increased, and easily
Cause carbon deposit coking reduction catalyst activity.Therefore, hydrotreated feed oil and product are all to hydrotreating techniques and hydrogenation
Treatment catalyst proposes requirement higher.
The geometric shape and physical dimension of catalyst, to fluid resistance, air velocity, the distribution of bed temperature gradient, concentration
Gradient distribution etc. all has a major impact.In order to give full play to the catalytic performance of catalyst, optimal profile and size should be selected,
This is accomplished by selecting most suitable forming method.Shaping of catalyst technology mainly include spray shaping, forming oil column, extrusion into
Type, compression molding and rotational forming etc..The fixed bed carried type hydrotreating catalyst for refining oil field of hydrogenation generally uses extrusion
Forming method.Need to add a certain amount of adhesive or diluted acid peptizing agent during extruded moulding, effect is to play bonding to make
With, it is ensured that shaping rear catalyst has certain geometry appearance shape and pressure-resistant, wear-resisting intensity higher.The preparation master of adhesive
If uniformly being mixed according to a certain percentage with oxide dry glue by diluted acid, agitated, ageing obtains jelly.
During catalyst or carrier extruded moulding, adhesive is generally using acid stronger non-volatile inorganic acid and hole
Hold the mixing jelly of less oxide.If CN93117528.3 is using the nothing of aluminum oxide, titanium oxide, silica and clay
Machine oxide or inorganic matter oxide mixture prepare adhesive with inorganic acid.US8,021,540 uses inorganic matter powdery group
It is shaping of catalyst adhesive to be allocated as, such as clay, montmorillonite, waterglass, and US7,687,676 directly use inorganic acid acid
The Ludox or Alumina gel of change are as the adhesive during shaping of catalyst.The effect of adhesive is by catalyst or carrier
Uniformly after mixing, peptization turns into the paste shape that can be squeezed to various components, at elevated pressures（Banded extruder）Extruded moulding is carried out, then
It is dried and calcination process.In dry and roasting process, in strong acid and small orifice oxide between the contact interface of each component
In the presence of chemically react, staggeredly connected chemical bond is formed each other, so that catalyst or carrier have one
Fixed geometric shape and pressure-resistant, wear-resisting intensity very high.The effect of wherein small orifice oxide is difficult in catalyst or carrier
Between the larger component of the pore volume of interaction, play a part of connection or grafting, it is combined closely each other, improve into
The mechanical strength of type rear catalyst or carrier.Have accordingly, as the acids needs that catalyst or carrier forming adhesive are used
Stronger acidity, and the noresidue impurity after being thermally decomposed；The small pore volume oxide for using then need with less granularity and
Pore volume.
Nitric acid have it is acid strong, easily decompose, price it is low, and after decomposing in the catalyst noresidue the advantages of, be to prepare
The most-often used inorganic acid of hydrogenation catalyst, and industrially small orifice oxide generally uses caking property in the most adhesive of application
Energy is good, prepare easy γ-aperture aluminum oxide precursor thing.CN97121663.0 give a kind of beta-zeolite molecular sieve catalyst and
Its preparation method, uses the aluminum oxide precursor thing of nitric acid and small pore volume in the preparation process of catalyst（Boehmite）Prepare
Adhesive, obtain preferable effect.But nitric acid will be discharged substantial amounts of NO in follow-up roasting process by thermal decompositionx, make
Into suitable environmental hazard, NOxBe be difficult purified treatment pollutant type, as restriction Catalyst Production link it is important because
One of element.NOxIt is a kind of main atmospheric pollutant, forms acid rain, photochemical fog and cause ozone hole
One of primary pollution source.In addition, a large amount of NOxGeneration also heavy corrosion can be caused to production equipment and operator's health is made
Into greatly infringement.According to statistics, often producing 1 ton of hydrogenation catalyst will produce about 45 standard cubic meter NOx, and these NOx are with relatively low dense
Degree is dispersed in Catalyst Production tail gas, forms a large amount of difficult emissions of volume.With flourishing for hydrogen addition technology,
The usage amount of hydrogenation catalyst is also rapidly increasing, and this also causes the pollution problem of NOx to aggravate with day, and the solution of this problem is
It is imperative.
With increasingly strict, the NO in solution catalyst preparation process of environmental lawxPollution problem increasingly receives pass
Note.For cleaning for catalyst production process, people have selected some cleaning nitrogenfree oxides in catalyst preparation process
The raw material of discharge.Therefore, the replacement acids of nitric acid is selected to the problem that attracts attention during shaping of catalyst.
CN00110016.5 and CN00123221.5 describe two kinds of oil refining class loaded catalyst extruded moulding methods respectively.In acidity
In the selection of peptizing agent, except that can use nitric acid as Aci-Jel solvent, two schemes are employed more inorganic and had
Machine acids is selected, and such as inorganic acid can select the combination of phosphoric acid, hydrochloric acid, sulfuric acid or several acid, and organic acid can be with formic acid, second
Acid, oxalic acid, citric acid etc..But in addition to nitric acid, most of inorganic acids, such as sulfuric acid, hydrochloric acid, hydrofluoric acid are equal after being thermally decomposed
Impurities left be there is, it is necessary to be post-processed, be not suitable for the peptizing agent directly as shaping of catalyst（Or peptization acid）.
For organic acid, majority thermally decomposed after noresidue element, but the wherein relatively low acetic acid of price, citric acid and acetic acid
Deng acid on the weak side, peptization performance is not strong, is not suitable for the peptizing agent separately as shaping of catalyst.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of catalyst carrier preparation method, by using Compound-acid, solution
The problem of contaminative exhaust emissions in catalyst carrier of having determined production process, while ensure that the performance of catalyst carrier.
The preparation process of catalyst carrier of the present invention includes following content：
（1）Mixed acid solution is prepared, phosphoric acid and organic acid are contained in mixed acid solution, the molar concentration of wherein phosphoric acid is
0.1~3.0mol/L, the molar concentration of organic acid is 0.2~5.0mol/L；
（2）Above-mentioned mixed acid solution mixes with oxide precursor, prepares adhesive；
（3）Step（2）Adhesive mix with catalyst support material powder, be then molded, dried, be calcined, obtain
To catalyst carrier.
In the inventive method, step（1）Described organic acid be formic acid, acetic acid, ethanedioic acid, citric acid, acetic acid it is a kind of or
It is several.In mixed acid solution, organic acid is 0.1 with the mol ratio of phosphoric acid:1~10.0:1.Organic acid soln is prepared first, will be had
Appropriate deionized water is added in machine acid, heating promotes dissolving, then lowers the temperature, and adds appropriate SPA molten in organic acid
Liquid, makes mixed acid solution.
In the inventive method, step（2）Middle oxide precursor is that catalyst field prepares adhesive conventional substances, such as small
One or more in hole boehmite, aperture silica gel, aperture magnesium hydroxide, aperture contained amorphous silica-alumina dry glue etc..Above-mentioned thing
The granularity requirement of matter is less than 100 mesh, preferably smaller than 180 mesh.Total acid and the mol ratio of oxide are 0.05 in adhesive:1~
3.0:1, preferably 0.05:1~1.8:1.Adhesive preparation method is well known to those skilled in the art, and specially mixed acid is molten
Liquid mixes with oxide precursor, stirs, and is aged 2~12 hours, obtains adhesive.
In the inventive method, step（3）Middle catalyst support component according to prepare catalyst specific requirement determine, typically
It is one kind in aluminum oxide, silica, magnesia, titanium oxide, zirconium oxide, amorphous silica-alumina, molecular sieve, activated carbon etc. or several
Kind.Support material can be above-mentioned carrier component in itself or carrier component precursor, the selection of carrier material and support material
It is the Conventional wisdom of those skilled in the art.In terms of oxide, weight percentage of the adhesive in final catalyst carrier
It is 3.0%~45.0%, preferably 7.0%~35.0%.Step（3）In, shaping, dry and roasting can use this area routine side
Method, is dried and is typically dried 2~48 hours at 50~200 DEG C, and roasting is general to be calcined 2~10 hours at 350~950 DEG C.
The catalyst carrier that the inventive method is obtained be shaped as bar shaped, cylindric, clover, bunge bedstraw herb, tooth ball or other
Irregular strip etc.；1.0~6.0mm of diameter, preferably 1.2~3.0mm, preferably 140 ~ 280N/cm of crushing strength, 160 ~ 240N/cm；Mill
Consumption intensity 0 ~ 2%；240 ~ 600m of specific surface area2/ g, preferably 300 ~ 480m2/g；0.30 ~ 1.00cm of pore volume3/ g, preferably 0.40 ~
0.80cm3/g；0.40 ~ 0.80g/cm of bulk density3, preferably 0.50 ~ 0.70g/cm3.Phosphorus content is 0.5% ~ 1.5%.
The present invention is directed to the NOx pollution problems of catalyst carrier production process, residual without ammonia nitrogen discharge, free from admixture from cleaning
The organic acid for staying eliminates the introducing of nitrate anion pollution sources as Aci-Jel solvent from source, has prepared organic acid and phosphorus
Sour mixed acid adhesive, can be widely applied to the preparation process using extruded moulding catalyst and catalyst carrier.
Although phosphoric acid can also generate phosphorus pentoxide residual in the catalyst after being thermally decomposed, P elements can be used as hydrogenation
The adjuvant component of catalyst, has certain modification to carrier surface, prevents the generation of nickel aluminate, also well
Cementation, is conducive to the preparation of hydrogenation catalyst and the performance of performance, is widely applied in hydrotreating catalyst.Cause
This, phosphoric acid can be used as cleaning inorganic acids as peptizing agent, but addition is subject to certain restrictions, excessive P elements
Residual can influence the pore structure of catalyst carrier.
When organic acid is used to prepare adhesive, because acid strength is weaker, it is impossible to obtain intensity and meet desired catalyst load
Body.Phosphoric acid belongs to middle strong acid, when only preparing adhesive with phosphoric acid, can not obtain intensity meet require catalyst, and with by
In the residual of P elements, the consumption of phosphoric acid is restricted, therefore cannot improve adhesive strength by improving the consumption of phosphoric acid
Mode improves catalyst carrier intensity.The present invention is by research, it has surprisingly been found that, lead to too small amount of phosphoric acid and match somebody with somebody with appropriate organic acid
Close, on the one hand can ensure that residuals are relatively low, meet the composition requirement of carrier, on the other hand can greatly improve the strong of carrier
Degree, solves the problems, such as that using organic acid high intensity catalyst carrier cannot be prepared.
Preparation method of the present invention is simple, it is easy to operate, and can be suitable for various extrusions with economic, environmental protection, efficient preparing
The preparation process of preformed catalyst or carrier, special-less process requirement, using can just realize whole lifes on existing equipment
Produce.
Specific embodiment
The present invention using organic acid and phosphoric acid Compound-acid as catalyst peptizing agent, the addition of a small amount of phosphoric acid just can be with
The acid weak deficiency of organic acid is made up, intensity can be prepared and met desired catalyst carrier, although P elements have element
The problem of residual, but a small amount of P elements will not bring negative impact to the performance of catalyst.
With reference to the preparation method of carrier of hydrogenating catalyst, the process of the inventive method is illustrated：
（1）Organic acid soln is prepared, 1320g oxalic acid is weighed（Ethanedioic acid）White crystal, is dissolved in 50 DEG C of steamings of constant temperature stirring
In distilled water, stir 20 minutes, add SPA 110mL, continue to stir and match somebody with somebody 20min, make transparent 5000mL mixed acid molten
Liquid.
（2）Weigh the small porous aluminum oxide 720g that butt is 72.2%.Small porous aluminum oxide is intended for commercially available Alchlor process prepares aperture
Boehmite, pore volume 0.32mL/g, specific surface area 286m2/ g, bulk density ~ 0.42g/cm3, granularity is less than 180 mesh.
（3）The mixed acid solution 1180mL in step 1 is measured to be slowly added into the mortar for placing small porous aluminum oxide, it is static
After 20min, stir, into white translucent paste shape, static ageing 8h, prepares this catalyst carrier and use and glue at room temperature
Mixture.
（4）Catalyst carrier key component macroporous aluminium oxide or contained amorphous silica-alumina dry glue product are crushed, sieving granularity is small
In 180 mesh, according to constant temperature at 600 DEG C 3 hours under conditions of, determine each component butt composition.
（5）Modified aluminas and contained amorphous silica-alumina dry glue powder, add extrusion aid or its auxiliary agent, auxiliary agent to be in proportion
One or more containing F, B, Zr and Ni compound, then carry out kneading, are sufficiently mixed it.
（6）Powder mixture addition adhesive is molded, then extrusion prepares carrier of hydrogenating catalyst.
Its forming method is extruded moulding, and banded extruder orifice plate can be cylinder, clover, bunge bedstraw herb or other abnormity, then carry out
Dry, be calcined, prepare carrier of hydrogenating catalyst.
Example 1（Referencing schemes）
Take 1280mL dilute nitric acid solutions（Concentration is 4g nitric acid/100mL）, it is gradually added into 720g aperture boehmites（Moral
State produces SB powder）, after static 20min, stir, into white translucent paste shape, static ageing 8h, prepares viscous at room temperature
Mixture.Take 580g macroporous aluminium oxides（Cut Noya Inc.'s production, pore volume 0.80mL/g, specific surface area 295m in Tianjin2/ g, butt
72.1%）, add 6g sesbania powders, and add 562.9g adhesives, roll 30 minutes, add appropriate distilled water, make mixture into
Paste shape, extrusion, a diameter of 1.5mm clover of banded extruder orifice plate can be squeezed.Wet bar is dried 4 hours at 120 DEG C, is then roasted
Burn, 550 DEG C of temperature, 3 hours time, numbering HT-1S.
Example 2（Referencing schemes）
The dilute nitric acid solution of example 1 is changed to acetic acid solution（Concentration is 13.2g acetic acid/100mL）, other are prepared with example 1
Go out carrier, numbering HT-2S.
Example 3（Referencing schemes）
The dilute nitric acid solution of example 1 is changed to citric acid solution（Concentration is 18.8g citric acids/100mL）, other with example 1,
Prepare carrier, numbering HT-3S.
Example 4（Referencing schemes）
The dilute nitric acid solution of example 1 is changed to acetic acid solution（Concentration is 26.4g acetic acid/100mL）, other are prepared with example 1
Go out carrier, numbering HT-4S-1.
The dilute nitric acid solution of example 1 is changed to phosphoric acid solution（0.8g phosphoric acid/100mL）, other prepare carrier with example 1,
Numbering HT-4S-2.
Example 5（Scheme of the invention）
The dilute nitric acid solution of example 1 is changed to acetic acid and phosphoric acid mixed solution（Concentration is 13.2g acetic acid/100mL+0.8g phosphorus
Acid/100mL）, other prepare carrier, numbering HT-5S with example 1.
Example 6（Scheme of the invention）
The dilute nitric acid solution of example 1 is changed to acetic acid and phosphoric acid mixed solution（Concentration is 13.2g acetic acid/100mL+1.5g phosphorus
Acid/100mL）, other prepare carrier, numbering HT-6S with example 1.
Example 7（Scheme of the invention）
The dilute nitric acid solution of example 1 is changed into citric acid and phosphoric acid mixed solution（Concentration is 18.8g citric acids/100mL+1.5g
Phosphoric acid/100mL）, other prepare carrier, numbering HT-6S with example 1.
Carrier HT-1S ~ 3S is comparison example, and HT-5S ~ 7S is present example, and physico-chemical property is listed in table 1, the carrier of example 4
Crushed substantially after roasting, intensity is very low.Carrier HT-S1 and HT-S6 are impregnated into molybdenum nickel phosphorus solution carries out supersaturated dipping, so
500 DEG C are calcined 3h afterwards, and numbering is HT-1 and HT-6.Catalyst physico-chemical property is shown in Table 2.
The physico-chemical property of the carrier of table 1.
| Numbering | HT-1S | HT-2S | HT-3S | HT-5S | HT-6S | HT-7S |
| Chemical composition, % | ||||||
| -- | -- | -- | 0.91 | 1.52 | 1.55 | |
| Physico-chemical property | ||||||
| Heap ratio, g/mL | 0.602 | 0.589 | 0.599 | 0.608 | 0.611 | 0.612 |
| Crushing strength, N/cm | 210 | 126 | 117 | 157 | 197 | 181 |
| Abrasion resistance, wt% | 0.8 | 1.4 | 1.9 | 1.1 | 0.9 | 0.7 |
| 324 | 335 | 344 | 347 | 315 | 362 | |
| 0.612 | 0.620 | 0.628 | 0.631 | 0.620 | 0.624 | |
| 7.4 | 8.2 | 8.0 | 8.8 | 8.4 | 8.6 | |
| Total acid content, Mmol/g | 0.41 | 0.38 | 0.56 | 0.57 | 0.54 | 0.64 |
RBETFor the average pore diameter that BET method is measured.
Strength detection, ZQJ-II Intelligent testing machine for particle.
The physico-chemical property of the catalyst of table 2.
| Numbering | HT-1 | HT-6 |
| Chemical composition, % | ||
| 23.4 | 22.6 | |
| NiO | 3.8 | 3.4 |
| 71.7 | 71.3 | |
| 1.1 | 2.7 | |
| Physico-chemical property | ||
| Heap ratio, g/mL | 0.841 | 0.856 |
| Crushing strength, N/cm | 212 | 204 |
| Abrasion resistance, wt% | 0.6 | 0.8 |
| 198 | 204 | |
| 0.341 | 0.356 |
In can be seen that the inventive method from embodiment data, place a small amount of phosphoric acid in organic acid soln, preparation it is viscous
Mixture can be used for preparing high intensity catalyst carrier, without harmful tailpipe emissions in production process.
Claims (10)
1. a kind of preparation method of catalyst carrier, it is characterised in that including following process：
（1）Prepare mixed acid solution, in mixed acid solution contain phosphoric acid and organic acid, wherein the molar concentration of phosphoric acid be 0.1~
3.0mol/L, the molar concentration of organic acid is 0.2~5.0mol/L；
（2）Above-mentioned mixed acid solution mixes with oxide precursor, prepares adhesive；In adhesive total acid and oxide mole
Than being 0.05~3.0；
（3）Step（2）Adhesive mix with catalyst support material powder, be then molded, dried, be calcined, urged
Agent carrier；
Step（1）In mixed acid solution, organic acid is 0.1~10.0 with the mol ratio of phosphoric acid；
Step（2）Middle oxide precursor is aperture boehmite, aperture silica gel, aperture magnesium hydroxide, aperture amorphous silicon
One or more in aluminium dry glue.
2. method according to claim 1, it is characterised in that：Step（1）Described organic acid is formic acid, acetic acid, second two
Acid, one or more in citric acid.
3. method according to claim 1, it is characterised in that：The granularity of oxide precursor is less than 100 mesh.
4. method according to claim 3, it is characterised in that：The granularity of oxide precursor is less than 180 mesh.
5. method according to claim 1, it is characterised in that：In adhesive the mol ratio of total acid and oxide for 0.05~
1.8。
6. method according to claim 1, it is characterised in that：Catalyst support component is aluminum oxide, silica, oxidation
One or more in magnesium, titanium oxide, zirconium oxide, amorphous silica-alumina, molecular sieve, activated carbon.
7. the method according to claim 1 or 6, it is characterised in that：Support material be carrier component in itself or carrier component
Precursor.
8. method according to claim 1, it is characterised in that：In terms of remaining oxide, adhesive is carried in final catalyst
Weight percentage in body is 3.0%~45.0%.
9. method according to claim 8, it is characterised in that：In terms of remaining oxide, adhesive is carried in final catalyst
Weight percentage in body is 7.0%~35.0%.
10. method according to claim 1, it is characterised in that：Step（3）In, dry dry at 50~200 DEG C 2~
48 hours, roasting was calcined 2~10 hours at 350~950 DEG C.
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