CN101347746B

CN101347746B - Catalyst for producing olefin hydrocarbon by catalytic pyrolysis of naphtha

Info

Publication number: CN101347746B
Application number: CN2007100439540A
Authority: CN
Inventors: 陈亮; 马广伟; 谢在库; 姚晖; 胡永君
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2007-07-18
Filing date: 2007-07-18
Publication date: 2011-04-27
Anticipated expiration: 2027-07-18
Also published as: CN101347746A

Abstract

The invention relates to a catalyst for catalytic cracking of naphtha to olefins, and the catalyst is mainly used for solving the problems of high using temperature and low yield of ethylene and propylene of the existing catalyst for preparing the ethylene and the propylene by the catalytic cracking. The catalyst adopts at least one element of IA family or IIA family in a periodic table of supported elements on a ZSM-5/mordenite symbiotic molecular sieve or a ZSM-5/Beta zeolite symbiotic molecular sieve or oxides thereof to compose the catalyst; therefore, the technical proposal can better solve the problems and can be used in the industrial production for preparing the ethylene and the propylene by catalytic cracking.

Description

The catalyst that is used for producing olefin hydrocarbon by catalytic pyrolysis of naphtha

Technical field

The present invention relates to a kind of catalyst that is used for producing olefin hydrocarbon by catalytic pyrolysis of naphtha.

Background technology

Along with the development of society, the market demand of China's ethylene, propylene sharply increases, and the import volume of ethylene, propylene and downstream product thereof increases year by year, and the home products occupation rate of market is less than half.Whole world ethene is raw material with naphtha (or ethane) mainly at present, adopts steam heat cracking technique (under the temperature about 800 ℃) production, and its output surpasses 90% of total output.Catalytic pyrolysis is compared with the steam heat cracking, and this process reaction temperature is than low 50～200 ℃ approximately of standard cracking reactions, and therefore than common steam cracking less energy consumption, cracking furnace pipe inwall coking rate will reduce, thereby but prolong operation cycle increases the boiler tube life-span; CO2 emission also can reduce, and can adjust the product mix flexibly, can increase the total recovery of ethene and propylene, and production cost of ethylene reduces significantly.

U.S. Pat P6211104 and domestic patent CN1504540A adopt a kind of 10～70 weight % clays that contain, 5～85 weight % inorganic oxides, 1～50 weight % molecular sieve is formed catalyst, various raw materials to traditional steam heat cracking, the activity, the especially ethene that well are converted into light olefin have been demonstrated.With molecular sieve be by 0～25 weight %Y zeolite of high silica alumina ratio or have the ZSM molecular sieve of MFI structure, form by phosphorus/Al, Mg or Ca dipping, but the ethylene, propylene selectivity of catalyst and yield are not high.

Japan Asahi Chemical Industry (patent CN1274342A) has announced that a kind of high silica alumina ratio, the molecular sieve of aperture between 0.5～0.65 nanometer are catalyst, be the feedstock production ethylene, propylene with the light hydrocarbons that contains alkene, but the ethylene, propylene yield is lower.

Exxon Mobil (00816642.0) announces that a kind of aperture of a kind of usefulness contains the hydrocarbon raw material of naphtha less than the zeolite treatment of 0.7 nanometer, produces ethylene, propylene between 550～600 ℃, and conversion of raw material is lower.

Mobil Oil Corporation (CN1413244A) has announced that a kind of mesopore phosphate material with modification is that catalyst and elementary catalytic pyrolysis material combine, the hydrocarbon raw material of catalytic pyrolysis sulfur-bearing prepares micromolecular hydrocarbon mixture, but the serviceability temperature of catalyst, conversion of raw material and product yield are all lower.

Summary of the invention

Technical problem to be solved by this invention is that the catalyst activity that uses in the existing naphtha catalytic pyrolysis preparing ethylene propylene reaction is lower, and the problem that the yield of ethylene, propylene is low, reaction temperature is high provides a kind of catalyst of new preparing ethylene propylene from catalytic pyrolysis.This catalyst has the catalytic activity height, ethylene propylene yield height, the advantage that reaction temperature is low.

For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst that is used for producing olefin hydrocarbon by catalytic pyrolysis of naphtha by weight percentage, comprises following active component:

A) at least a in the coexisting molecular sieve of 80～99.5% coexisting molecular sieve that is selected from ZSM-5 and modenite or ZSM-5 and β zeolite; With carry thereon

B) surplus is selected from the periodic table of elements at least a element or its oxide in IA family or the IIA family.

In the technique scheme, coexisting molecular sieve is at least a in ZSM-5/ mercerization zeolite symbiosis molecular screen or the ZSM-5/ beta zeolite coexisting molecular sieve; The weight percentage preferable range of ZSM-5 is 60～99.5% in the used coexisting molecular sieve, and more preferably scope 80～99%; The silica alumina ratio preferable range of used coexisting molecular sieve is 10～300, and more preferably scope is 12～50; The consumption preferable range of coexisting molecular sieve is 85～99% by weight percentage.IA family element preferred version is selected from least a among Li, K, Rb or the Cs, and more preferably scheme is to be selected from least a among Li or the K; IIA family element preferred version is to be selected from least a among Be, Mg, Ca, Sr or the Ba, and more preferably scheme is to be selected from least a among Mg or the Ca; The consumption preferable range of IA family element or IIA family element is 0.5～10% by weight percentage.The catalyst preferred version is also to comprise at least a or its oxide that is selected from periodic table of elements IVB family's element or the VB family element in the catalyst; IVB family element preferred version is selected from least a among Ti, Zr or the Hf; VB family element preferred version is selected from least a among V, Nb or the Ta; Be selected from the consumption preferable range 0.01～2% of at least a or its oxide in periodic table of elements IVB family's element or the VB family element by weight percentage, more preferably scope is 0.1～1%.

The raw material that the preparation coexisting molecular sieve uses: the silicon source is metasilicate, silicate sodium or Ludox, the aluminium source is aluminium salt or aluminate, the template agent is at least a in 4-propyl bromide, TPAOH, triethylamine, n-butylamine, tetraethyl ammonium hydroxide, ethylenediamine or the ethamine, and the pH value of regulating colloidal sol with diluted acid is 10～13.The coexisting molecular sieve modification is with the acid solution and the salting liquid of corresponding active component element.

The synthetic method of coexisting molecular sieve is, get the silicon source and the aluminium source of aequum by material proportion, make solution with dissolved in distilled water respectively, then two kinds of solution are mixed, the powerful stirring adds one or more template agent of aequum then, stirs after 30 minutes with rare acid for adjusting pH value in 10～13 scopes, supply distilled water again, add the corresponding crystal seed of aequum.Colloidal sol is put into autoclave, control temperature crystallization a period of time of 120～180 ℃ after, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours, can obtain corresponding coexisting molecular sieve.With concentration is 5% ammonium nitrate solution, and 70 ℃ of exchanges twice, 550 ℃ of roastings are 3 hours then, repeat twice after, make the Hydrogen coexisting molecular sieve.

The present invention since adopted acid strong, have multi-stage artery structure, ethylene, propylene selectivity good coexisting molecular sieve be carrier, select for use the alkali metal modified molecular screen to regulate the acidity of coexisting molecular sieve, strengthen the stability of molecular sieve and the selectivity of ethylene, propylene, and the ratio that can regulate ethylene, propylene.Select for use transition metal that coexisting molecular sieve is carried out modification with the easy transition of the big electronics of charge density, strengthen the stable and acid of coexisting molecular sieve, make the catalyst acid density that makes big, the acid strength height, acid stable is difficult for running off, the ethylene, propylene selectivity is good, is suitable for alkane cracking and becomes ethylene, propylene.

In order to check and rate activity of such catalysts, the related catalyst compressing tablet of invention, break into pieces, sieve after, get 20～40 purpose particles with standby.The C that adopts Shanghai Gaoqiao petro-chemical corporation to produce ₄～C ₁₀The naphtha of hydrocarbon is a raw material, naphtha physical index such as table 1.With internal diameter is 12 millimeters down examination of fixed bed reactors normal pressure, is 600～650 ℃ in reaction temperature, and reaction pressure is 0.001MPa～0.5MPa, weight space velocity 0.25～4 hour ^-1, under the condition of water/feedstock oil weight ratio 1～4: 1, naphtha being carried out catalytic pyrolysis, the ethylene, propylene yield can reach 54%, has obtained better technical effect.

Table 1 feed naphtha index

Project	Data
		Density (20 ℃) kilogram/rice ³	704.6
Boiling range is boiling range ℃ just	40
		Whole boiling range ℃	160
Saturated vapor pressure (20 ℃) kPa	50.2
		Alkane % (weight %)	65.18
N-alkane % (weight %) in the alkane	>32.5
		Cycloalkane % (weight %)	28.44
Alkene % (weight %)	0.17
		Aromatic hydrocarbons % (weight %)	6.21

The present invention is further elaborated below by embodiment.

The specific embodiment

[embodiment 1]

Get 284 gram sodium metasilicates, become solution A with 300 gram dissolved in distilled water, get 33.3 gram aluminum sulfate, make solution B with 100 gram distilled water, B solution is slowly poured in the A solution, the powerful stirring, add 24.4 gram ethylenediamines then, after stirring a period of time, regulate the pH value 11.5 with dilute sulfuric acid, the mole proportioning of control colloidal sol is: Si: Al: ethylenediamine: H ₂O=1: 0.1: 0.4: 40, add the crystal seed that contains ZSM-5 and modenite presoma, stir and after 30 minutes mixed solution is put into autoclave, 180 ℃ of insulations 40 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make the coexisting molecular sieve of ZSM-5 and modenite, with the XRD diffraction quantitatively as can be known in the coexisting molecular sieve ZSM-5 and modenite weight content be respectively 95% and 5%.With concentration is 5% ammonium nitrate solution, and 70 ℃ of exchanges twice, 550 ℃ of roastings are 3 hours then, repeat twice after, make Hydrogen ZSM-5 and mercerization zeolite symbiosis molecular screen, be designated as FH-1.

[embodiment 2]

Get 284 gram sodium metasilicates, become solution A with 300 gram dissolved in distilled water, get 16.7 gram aluminum sulfate, make solution B with 100 gram distilled water, B solution is slowly poured in the A solution, the powerful stirring, add 12.2 gram ethylenediamines and 29.4 gram tetraethyl ammonium hydroxides (mixed templates is designated as M) then, after stirring a period of time, regulate the pH value 11 with dilute sulfuric acid, the mole proportioning of control colloidal sol is: Si: Al: M: H ₂O=1: 0.05: 0.4: 40, add 2.8 gram β zeolite seed crystals, mixed solution is put into autoclave, 160 ℃ of insulations 40 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make ZSM-5/ beta zeolite coexisting molecular sieve, with the XRD diffraction quantitatively as can be known in the coexisting molecular sieve ZSM-5 weight percentage be 94.6%, the β zeolite is 5.4%.With concentration is 5% ammonium nitrate solution, and 70 ℃ of exchanges twice, 550 ℃ of roastings are 3 hours then, repeat twice after, make Hydrogen ZSM-5/ beta zeolite coexisting molecular sieve, be designated as FH-2.

[embodiment 3]

Get 284 gram sodium metasilicates, become solution A with 300 gram dissolved in distilled water, get 33.3 gram aluminum sulfate, make solution B with 100 gram distilled water, B solution is slowly poured in the A solution, the powerful stirring, add 24.4 gram ethylenediamines then, stir after 20 minutes, regulate the pH value 11.5 with dilute sulfuric acid, the mole proportioning of control colloidal sol is: Si: Al: ethylenediamine: H ₂O=1: 0.1: 0.4: 40, add 2.8 gram Y zeolite seed crystals, mixed solution is put into autoclave, 130 ℃ of insulations 40 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make ZSM-5/Y zeolite coexisting molecular sieve.Quantitatively contain the ZSM-5 of 94.5% weight and the Y zeolite of 5.5% weight in the coexisting molecular sieve as can be known with the XRD diffraction.With concentration is 5% ammonium nitrate solution, and 70 ℃ of exchanges twice, 550 ℃ of roastings are 3 hours then, repeat twice after, make Hydrogen ZSM-5/Y zeolite coexisting molecular sieve, be designated as FH-3.

[embodiment 4～7]

The Hydrogen ZSM-5/Y zeolite coexisting molecular sieve that the Hydrogen ZSM-5/ mercerization zeolite symbiosis molecular screen that embodiment 1 is made, the Hydrogen ZSM-5/ beta zeolite coexisting molecular sieve that embodiment 2 makes and embodiment 3 make mixes according to a certain percentage, make mechanical impurity, as shown in table 2.

Table 2

Embodiment	The coexisting molecular sieve kind	Ratio (weight ratio)	Sample number into spectrum
				Embodiment 4	ZSM-5/ modenite+ZSM-5/ β zeolite	1∶1	FH-4
Embodiment 5	ZSM-5/ modenite+ZSM-5/Y zeolite	1∶1	FH-5
				Embodiment 6	ZSM-5/ β zeolite+ZSM-5/Y zeolite	1∶1	FH-6
Embodiment 7	ZSM-5/ modenite+ZSM-5/ β zeolite+ZSM-5/Y zeolite	1∶1∶1?	FH-7?

[embodiment 8～25]

According to the method for embodiment 1, embodiment 2 and embodiment 3,, make a collection of Hydrogen coexisting molecular sieve respectively by changing the amount of raw material proportioning, pH value and adding crystal seed, as shown in table 3.

Table 3

Embodiment	The coexisting molecular sieve type	SiO ₂/Al ₂O ₃Mol ratio	ZSM-5 content (weight %)	Sample number into spectrum
					Embodiment 8	The ZSM-5/ modenite	12	61.5	FH-8
Embodiment 9	The ZSM-5/ modenite	16	73.6	FH-9
					Embodiment 10	The ZSM-5/ modenite	40	85.4	FH-10
Embodiment 11	The ZSM-5/ modenite	100	96.8	FH-11
					Embodiment 12	The ZSM-5/ modenite	300	99.2	FH-12
Embodiment 13	The ZSM-5/ modenite	20	90.1	FH-13
					Embodiment 14	ZSM-5/ β zeolite	12	98.0	FH-14
Embodiment 15	ZSM-5/ β zeolite	20	90.4	FH-15
					Embodiment 16	ZSM-5/ β zeolite	60	60.5	FH-16
Embodiment 17	ZSM-5/ β zeolite	100	74.6	FH-17
					Embodiment 18	ZSM-5/ β zeolite	300	85.3	FH-18
Embodiment 19	ZSM-5/ β zeolite	40	99.0	FH-19
					Embodiment 20	The ZSM-5/Y zeolite	12	60.2	FH-20
Embodiment 21	The ZSM-5/Y zeolite	16	71.8	FH-21
					Embodiment 22	The ZSM-5/Y zeolite	50	85.3	FH-22
Embodiment 23	The ZSM-5/Y zeolite	100	97.3	FH-23
					Embodiment 24	The ZSM-5/Y zeolite	300	99.5	FH-24
Embodiment 25	The ZSM-5/Y zeolite	20	91.0	FH-25

[embodiment 26]

Get ZSM-5/ mercerization zeolite symbiosis molecular screen 20 grams that embodiment 1 makes, add 167 milliliters of the magnesium nitrates of 0.1 mol, stir evaporates to dryness at 70 ℃ then, behind the drying and roasting, make magnesium-modified ZSM-5/ mercerization zeolite symbiosis molecular screen catalyst.The catalyst compressing tablet, break into pieces, sieve after, get 20～40 purpose particles and put into fixed bed reactors, be 0.02MPa, weight space velocity 1 hour in 650 ℃ of reaction temperatures, reaction pressure ^-1, check and rate under water/condition of 3: 1 of naphtha weight ratio, the results are shown in Table 4.

[embodiment 27～33]

Get the coexisting molecular sieve of different the foregoing description preparation,, make catalyst and appraisal result is as shown in table 4 according to method modification and the examination of embodiment 26.

[embodiment 34]

Get ZSM-5/Y zeolite coexisting molecular sieve 20 grams that embodiment 22 makes, 84 milliliters of magnesium nitrates that add 0.1 mol add 50 milliliters in the calcium nitrate of 0.1 mol again, stir evaporates to dryness at 70 ℃ then, behind the drying and roasting, make the ZSM-5/Y zeolite coexisting molecular sieve catalyst of magnesium and calcium modification.Method examination according to embodiment 26 the results are shown in Table 4.

[embodiment 35～38]

Get the coexisting molecular sieve of different the foregoing description preparation,, make catalyst and appraisal result is as shown in table 4 according to method modification and the examination of embodiment 34.

Table 4

Embodiment	The numbering of specimen in use	The type of modifying element and content (weight %)	Yield of ethene (weight %)	Propene yield (weight %)	Diene yield (weight %)
						Embodiment 26	FH-1	2％Mg	27.23	26.36	53.59
Embodiment 27	FH-2	6％Ca	25.29	26.87	52.16
						Embodiment 28	FH-5	0.1％Be	28.74	24.58	53.32
Embodiment 29	FH-8	10％Mg	22.55	22.72	45.27
						Embodiment 30	FH-11	0.5％Sr	26.33	25.75	52.08
Embodiment 31	FH-15	1％Ba	25.36	24.93	50.29
						Embodiment 32	FH-17	0.5％Li	24.82	25.44	50.26
Embodiment 33	FH-20	1％K	24.89	22.47	47.36
						Embodiment 34	FH-22	1％Mg+1％Ca	25.19	23.34	48.53
Embodiment 35	FH-23	2％Li+2％K	27.22	24.41	51.63
						Embodiment 36	FH-3	4％Mg+4％K	26.32	25.45	51.77
Embodiment 37	FH-4	2％Mg+2％Ca+2％K	23.90	28.16	52.06
						Embodiment 38	FH-7	2％Mg+2％Ca+2％Li+2％K	26.35	28.11	54.46

[embodiment 39～52]

Get the coexisting molecular sieve of different the foregoing description preparation,, make catalyst and appraisal result is as shown in table 5 according to method modification and the examination of embodiment 34.

Table 5

Embodiment	The numbering of specimen in use	The type of modifying element and content (weight %)	Yield of ethene (weight %)	Propene yield (weight %)	Diene yield (weight %)
						Embodiment 39	FH-9	2％Mg+1％Ti	21.54	28.63	50.17
Embodiment 40	FH-10	4％Ca+0.5％Zr	21.76	30.31	52.07
						Embodiment 41	FH-12	10％Mg+0.2％Hf	21.24	25.75	46.99
Embodiment 42	FH-13	0.5％Ba+0.2％Zr+0.6％Ti	28.87	24.23	53.10
						Embodiment 43	FH-14	1％Mg+0.2％Ti+0.2％Zr+0.2％Hf	28.65	24.12	52.77
Embodiment 44	FH-16	2％Mg+2％Ca+0.5％Ti+0.5％Zr	20.76	28.25	49.01
						Embodiment 45	FH-18	0.5％Ca+0.5％V	17.94	29.69	47.63
Embodiment 46	FH-21	1％Ba+0.2％Nb	22.45	26.86	49.31
						Embodiment 47	FH-24	0.5％Mg+0.5％V+0.5％Nb+0.5％Ta	28.10	22.97	51.07
Embodiment 48	FH-25	2％Mg+2％Ca+0.2％V+0.2％Nb	28.88	24.65	53.53
						Embodiment 49	FH-6	0.5％Mg+0.5％Ti+0.5％V	24.02	28.87	52.89
Embodiment 50	FH-19	1％Mg+1％Ca+0.2％Zr+0.2％Nb	28.36	25.20	53.56
						Embodiment 51	FH-1?	2％Mg+2％Ca+0.2％Ti+0.2％Zr?+0.2％V+0.2％Nb	27.47?	26.93?	54.40?
Embodiment 52	FH-3?	2％Mg+2％Ca+0.2％Ti+0.2％Hf?0.2％Zr+0.2％V+0.2％Nb+0.2％Ta	27.55?	27.34?	54.89?

[comparative example 1]

Get the SiO that Shanghai petrochemical industry research institute produces ₂/ Al ₂O ₃Mol ratio is 40 ZSM-5 molecular sieve, according to the method modification of embodiment 40, makes the catalyst of calcium and modified zirconia, checks and rates result such as table 6 according to the mode of embodiment 40.

[comparative example 2]

Get the SiO that Shanghai petrochemical industry research institute produces ₂/ Al ₂O ₃Mol ratio is 20 modenite, according to the method modification of embodiment 42, makes the catalyst of barium, zirconium and titanium modification, checks and rates result such as table 6 according to the mode of embodiment 42.

[comparative example 3]

Get the SiO that Shanghai petrochemical industry research institute produces ₂/ Al ₂O ₃Mol ratio is 40 β zeolite, according to the method modification of embodiment 50, makes the catalyst of magnesium, calcium, zirconium and niobium modification, checks and rates result such as table 6 according to the mode of embodiment 50.

[comparative example 4]

Get the SiO that Shanghai petrochemical industry research institute produces ₂/ Al ₂O ₃Mol ratio is 20 Y zeolite, according to the method modification of embodiment 48, makes the catalyst of magnesium, calcium, vanadium and niobium modification, checks and rates result such as table 6 according to the mode of embodiment 48.

Table 6

Comparative example	Used molecular sieve type	The type of modifying element and content (weight %)	Yield of ethene (weight %)	Propene yield (weight %)	Diene yield (weight %)
						Comparative example 1	ZSM-5	4％Ca+0.5％Zr	22.45	23.22	45.67
Comparative example 2	Modenite	0.5％Ba+0.2％Zr+0.6％Ti	21.78	22.74	44.52
						Comparative example 3	The β zeolite	1％Mg+1％Ca+0.2％Zr+0.2％Nb	21.26	22.48	43.74
Comparative example 4	The Y zeolite	2％Mg+2％Ca+0.2％V+0.2％Nb	20.69	21.53	42.22

Claims

1. catalyst that is used for producing olefin hydrocarbon by catalytic pyrolysis of naphtha, form by following active component by weight percentage:

B) surplus is selected from the periodic table of elements at least a element or its oxide in I A family or the II A family;

Wherein, in the described coexisting molecular sieve, the weight percentage of ZSM-5 molecular sieve is 60～99.5%; The SiO of coexisting molecular sieve ₂/ Al ₂O ₃Mol ratio is 10～300.

2. according to the described catalyst that is used for producing olefin hydrocarbon by catalytic pyrolysis of naphtha of claim 1, it is characterized in that the coexisting molecular sieve consumption is 85～99% by weight percentage.

3. according to the described catalyst that is used for producing olefin hydrocarbon by catalytic pyrolysis of naphtha of claim 2, it is characterized in that the SiO of coexisting molecular sieve ₂/ Al ₂O ₃Mol ratio is 12～50; The weight percentage of ZSM-5 molecular sieve is 80～99%.

4. according to the described catalyst that is used for producing olefin hydrocarbon by catalytic pyrolysis of naphtha of claim 1, it is characterized in that I A family element is selected from least a among Li, K, Rb or the Cs; II A family element is selected from least a among Be, Mg, Ca, Sr or the Ba; The consumption that is selected from least a element in periodic table of elements I A family or the II A family or its oxide by weight percentage is 0.5～10%, and a and b two component sums satisfy 100%.

5. catalyst that is used for producing olefin hydrocarbon by catalytic pyrolysis of naphtha, form by following active component by weight percentage:

B) be selected from least a or its oxide in periodic table of elements IV B family's element or the V B family element, and surplus be selected from the periodic table of elements at least a element or its oxide in I A family or the II A family;

6. according to the described catalyst that is used for producing olefin hydrocarbon by catalytic pyrolysis of naphtha of claim 5, it is characterized in that IV B family element is selected from least a among Ti, Zr or the Hf; V B family element is selected from least a among V, Nb or the Ta.

7. according to the described catalyst that is used for producing olefin hydrocarbon by catalytic pyrolysis of naphtha of claim 5, the consumption at least a or its oxide that it is characterized in that being selected from by weight percentage in periodic table of elements IV B family's element or the V B family element is 0.01～2%.

8. according to the described catalyst that is used for producing olefin hydrocarbon by catalytic pyrolysis of naphtha of claim 7, the consumption at least a or its oxide that it is characterized in that being selected from by weight percentage in periodic table of elements IV B family's element or the V B family element is 0.1～1%.